Narrow Absorbing Polymer Nanoparticles and Related Methods
By combining absorbent and emitter monomer units in polymer nanoparticles, the absorption width of the nanoparticles is controlled, and the contradiction between the brightness and absorption cross-section of the nanoparticles in the prior art is solved, and the effects of high quantum yield and narrowband absorption are achieved.
Patent Information
- Application Number
- CN201980060997.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Priority Date
- 2018-09-18
- Filing Date
- 2019-09-16
- Publication Date
- 2025-06-17
- Estimated Expiration
- 2039-09-16
AI Technical Summary
Existing polymer nanoparticles have wide absorption bands, resulting in difficult trade-offs between quantum yield and absorption cross-section, reducing overall brightness, and possible fluorescence self-quenching problems in condensed states.
Polymer nanoparticles with narrow band absorption were developed, and the absorption width near the maximum absorbance value of the nanoparticles is controlled to be less than 150 nm by combining absorbent monomer units and emitter monomer units in the nanoparticles.
The quantum yield and brightness of nanoparticles are achieved, while maintaining the narrowband absorption characteristics, solving the contradiction between brightness improvement and absorption cross-section reduction in the prior art.
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Figure CN112740018B_ABST
Abstract
Description
[0001] Cross - reference to related applications
[0002] This application claims the benefit of U.S. Patent Application No. 62 / 733,009, filed on September 18, 2018, the entire disclosure of which is hereby incorporated by reference in its entirety.
[0003] Statement of government licensing rights
[0004] This invention was made with government support under Grant No. R01MH115767 awarded by the National Institutes of Health (NIH). The government has certain rights in this invention. Background of the invention
[0005] Fluorescence imaging is a non - invasive, real - time, high - resolution, and non - radioactive visualization system for basic research and clinical applications. Polymer nanoparticles are a class of photon - emitting probes of interest. However, most polymer nanoparticles have broad absorption bands. Additionally, most polymer nanoparticles require a trade - off between quantum yield and absorption cross - section, which may reduce overall brightness. Polymer dots may have fluorescence self - quenching in their condensed state, and low absorption cross - section limits the improvement of brightness. Summary of the invention
[0006] This summary is provided to introduce some concepts in a simplified form that will be further described in the detailed description below. This summary is not intended to identify key features of the claimed subject matter nor to be used to assist in determining the scope of the claimed subject matter.
[0007] The present disclosure provides polymer nanoparticles having narrow - band absorption, methods of preparing polymer nanoparticles having narrow - band absorption, and methods of using polymer nanoparticles having narrow - band absorption.
[0008] In one aspect, the present disclosure features nanoparticles comprising a polymer that includes absorptive monomer units and emissive monomer units; wherein the absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum is less than 150 nm. The nanoparticles may further include one or more monomer units different from the absorptive monomer units and the emissive monomer units (a third or additional monomer unit different from the absorptive monomer units and the emissive monomer units). In some aspects, the absorptive monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In some embodiments, the absorptive monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof.
[0009] In another aspect, the present disclosure provides nanoparticles comprising a polymer, the polymer comprising absorbent monomer units and emissive monomer units, the absorbent monomer units may include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof. In some aspects, the absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum is less than 150 nm.
[0010] In another aspect, the present disclosure features nanoparticles comprising a polymer, the polymer comprising a first absorbent monomer unit; an emissive monomer unit; and one or more monomer units different from the absorbent monomer units and the emissive monomer units. The absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum may be less than 150 nm.
[0011] In some embodiments, the polymer has a backbone comprising absorbent monomer units, has side chains comprising absorbent monomer units, has termini comprising absorbent monomer units, or any combination thereof. The absorbent monomer units are covalently bonded to the polymer.
[0012] In various embodiments, the present disclosure provides nanoparticles comprising a first polymer having absorbent monomer units and a second polymer having emissive monomer units, wherein the absorption width of the nanoparticles at 15% of the absorbance maximum is less than 150 nm. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof.
[0013] In various embodiments, the present disclosure provides nanoparticles that include a first polymer having absorptive monomer units, the absorptive monomer units including BODIPY, BODIPY derivatives, or any combination thereof. In some embodiments, the absorptive monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof; and a second polymer having emissive monomer units. In some embodiments, the nanoparticles have an absorption width less than 150 nm at 10% (or in some embodiments, at 15%) of the absorbance maximum.
[0014] In some embodiments, the first polymer and the second polymer are the same polymer. In certain embodiments, the first polymer has a backbone including absorptive monomer units, has side chains including absorptive monomer units, has termini including absorptive monomer units, or any combination thereof. In some embodiments, the first polymer is a semiconductor polymer, the second polymer is a semiconductor polymer, or both the first polymer and the second polymer are semiconductor polymers. In certain embodiments, the mass ratio of the first polymer to the second polymer is greater than 1:1, greater than 2:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1, greater than 8:1, greater than 9:1, greater than 10:1, greater than 20:1, greater than 30:1, greater than 40:1, greater than 50:1, or greater than 100:1.
[0015] In certain embodiments, the nanoparticles further include a matrix, which may include a matrix polymer. In some embodiments, the matrix polymer is a non-semiconductor polymer. In certain embodiments, the matrix polymer is a semiconductor polymer.
[0016] In some embodiments, as measured by dynamic light scattering, the diameter of the nanoparticles is less than 1000 nm, less than 900 nm, less than 800 nm, less than 700 nm, less than 600 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 150 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, or less than 10 nm, as measured by dynamic light scattering. In certain embodiments, the quantum yield of the nanoparticles is greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, or greater than 50%.
[0017] In some embodiments, the absorbent monomer units are 30% or less, 25% or less, 20% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8%, 7% or less, 6% or less, or 5% or less of the total mass of the nanoparticles. In certain embodiments, the absorbent monomer units are 30% or more, 25% or more, 20% or more, 15% or more, 14% or more, 13% or more, 12% or more, 11% or more, 10% or more, 9% or more, 8% or more, 7% or more, 6% or more, or 5% or more of the total mass of the nanoparticles.
[0018] In certain embodiments, the nanoparticles comprise a blend of polymers. In some embodiments, the ratio of emissive monomer units to absorbent monomer units is less than 1:2, less than 1:3, less than 1:4, less than 1:5, less than 1:6, less than 1:7, less than 1:8, less than 1:9, less than 1:10, less than 1:11, less than 1:12, less than 1:13, less than 1:14, less than 1:15, less than 1:16, less than 1:17, less than 1:18, less than 1:19, less than 1:20, less than 1:25, less than 1:30, less than 1:35, less than 1:40, less than 1:50, less than 1:60, less than 1:70, less than 1:80, less than 1:90 or less than 1:100.
[0019] In some embodiments, the absorption width of the nanoparticles at 15% of the absorbance maximum, at 14% of the absorbance maximum, at 13% of the absorbance maximum, at 12% of the absorbance maximum, at 11% of the absorbance maximum, at 10% of the absorbance maximum, at 9% of the absorbance maximum, at 8% of the absorbance maximum, at 7% of the absorbance maximum, at 6% of the absorbance maximum, at 5% of the absorbance maximum, at 4% of the absorbance maximum, at 3% of the absorbance maximum, at 2% of the absorbance maximum, or at 1% of the absorbance maximum is less than 150 nm. In certain embodiments, the absorption width of the nanoparticles at 10% of the absorbance maximum is less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, or less than 70 nm. In some embodiments, the absorption width of the nanoparticles at 10% of the absorbance maximum is from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm.
[0020] In certain embodiments, the nanoparticles are bioconjugated to a biomolecule. In some embodiments, the biomolecule includes a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof. In some embodiments, the biomolecule includes an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof. In certain embodiments, the biomolecule includes streptavidin.
[0021] In some embodiments, the brightness of the nanoparticles is greater than 1.0×10 -13 cm 2 , which is calculated as the product of the quantum yield and the absorption cross-section.
[0022] In some embodiments, the nanoparticles do not include a β-phase structure. In certain embodiments, the nanoparticles do not include a fluorene monomer unit.
[0023] In various embodiments, the present disclosure provides methods for preparing the nanoparticles of the present disclosure, including: providing a solution comprising a polymer that includes absorbent monomer units and emissive monomer units, the absorbent monomer units including BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof; and collapsing the polymer to form nanoparticles. In some embodiments, the absorbent monomer units can include, for example, BODIPY, BODIPY derivatives, or any combination thereof. In certain embodiments, the nanoparticles have an absorption width at 10% (or in some embodiments, at 15%) of the absorbance maximum that is less than 150 nm. In some embodiments, the polymer has a backbone that includes absorbent monomer units, has side chains that include absorbent monomer units, has termini that include absorbent monomer units, or any combination thereof.
[0024] In various embodiments, the present disclosure provides methods for preparing the nanoparticles of the present disclosure, the method including: providing a solution comprising a first polymer and a second polymer, the first polymer including absorbent monomer units and the second polymer including emissive monomer units; collapsing the first polymer and the second polymer to form nanoparticles. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In certain embodiments, the first polymer has a backbone that includes absorbent monomer units, has side chains that include absorbent monomer units, has termini that include absorbent monomer units, or any combination thereof.
[0025] In certain embodiments, the collapsing step includes combining the solution with an aqueous liquid. In some embodiments, the nanoparticles are formed by nanoprecipitation.
[0026] In certain embodiments, the solution comprises 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by weight of absorbent monomer units. In some embodiments, the solution comprises 15% or more, 14% or more, 13% or more, 12% or more, 11% or more, 10% or more, 9% or more, 8% or more, 7% or more, 6% or more, 5% or more, 4% or more, 3% or more, 2% or more, or 1% or more by weight of absorbent monomer units.
[0027] In certain embodiments, the quantum yield of the nanoparticles is greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, or greater than 50%.
[0028] In various embodiments, the present disclosure provides methods for analyzing biomolecules, the methods comprising optically detecting the presence or absence of a biomolecule, wherein the biomolecule is attached to a nanoparticle as described above, and wherein the detection uses a detector.
[0029] In some embodiments, the method further comprises imaging the biomolecule, wherein the detector comprises an imaging device. In certain embodiments, the detector is selected from cameras, electron multipliers, charge-coupled device (CCD) image sensors, photomultiplier tubes (PMT), avalanche photodiodes (APD), single-photon avalanche diodes (SPAD), and complementary metal-oxide-semiconductor (CMOS) image sensors. In certain embodiments, the detector comprises a light, electrical, acoustic, or magnetic detector. In some embodiments, the detector incorporates fluorescence microscopy imaging.
[0030] In some embodiments, the method further comprises performing an assay. In certain embodiments, the assay is a digital assay. In some embodiments, the assay includes fluorescence-activated sorting. In certain embodiments, the assay includes flow cytometry. In some embodiments, the assay includes RNA extraction (with or without amplification), cDNA synthesis (reverse transcription), gene microarray, DNA extraction, polymerase chain reaction (PCR) (single, nested, real-time quantitative or ligation-mediated), isothermal nucleic acid amplification, DNA methylation analysis, cell culture, comparative genomic hybridization (CGH) studies, electrophoresis, Southern blot analysis, enzyme-linked immunosorbent assay (ELISA), digital nucleic acid assay, digital protein assay, assays for determining microRNA and siRNA content, assays for determining DNA / RNA content, assays for determining lipid content, assays for determining protein content, assays for determining carbohydrate content, functional cell assays, or any combination thereof.
[0031] In certain embodiments, the method further comprises amplifying a biomolecule to produce an amplification product, the amplification comprising performing polymerase chain reaction (PCR), isothermal nucleic acid amplification, rolling circle amplification (RCA), nucleic acid sequence-based amplification (NASBA), loop-mediated amplification (LAMP), strand displacement amplification (SDA), or any combination thereof. In certain embodiments, multiple biomolecules are analyzed and, as described above, at least a portion of the multiple biomolecules are attached to nanoparticles. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated when considered in conjunction with the accompanying drawings, in which:
[0033] Figures 1A to 1L is a non-limiting example of the schematic structure of a narrowband absorbent polymer.
[0034] Figure 1A Shows the structure of a homopolymer comprising only one narrowband absorbent monomer unit.
[0035] Figure 1B Shows the structure of a two-unit copolymer that includes one absorbent monomer unit (e.g., a narrowband absorbent monomer unit) and one common monomer unit.
[0036] Figure 1C Shows the structure of a three-unit copolymer that includes one absorbent monomer unit and two common monomer units such as common monomer unit 1 (G1) and common monomer unit 2 (G2).
[0037] Figure 1DShows the structure of a dual-unit copolymer comprising an absorbent unit crosslinked to a side chain.
[0038] Figure 1E Shows the structure of a homopolymer comprising an absorbent unit crosslinked to a side chain.
[0039] Figure 1F Shows the structure of a polymer comprising an absorbent unit attached to the polymer end.
[0040] Figure 1G Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0041] Figure 1H Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0042] Fig. 1I Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0043] Figure 1J Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0044] Figure 1K Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0045] Figure 1L Shows an exemplary schematic structure of an absorbent polymer comprising a general monomer unit, an absorbent monomer unit, and a functional monomer unit (or functional group).
[0046] Figures 2A to 2L Shows a non-limiting example of the schematic structure of a light-emitting polymer.
[0047] Figure 2A Shows the structure of a homopolymer comprising only one narrow-band emissive monomer unit.
[0048] Figure 2B Shows the structure of a dual-unit copolymer comprising one emissive monomer unit and one general monomer unit.
[0049] Figure 2CShows the structure of a terpolymer comprising an emissive monomer unit and two common monomer units such as common monomer unit 1 (G1) and common monomer unit 2 (G2).
[0050] Figure 2D Shows the structure of a binary copolymer comprising an emissive unit crosslinked to a side chain.
[0051] Figure 2E Shows the structure of a homopolymer comprising an emissive unit crosslinked to a side chain.
[0052] Figure 2F Shows the structure of a polymer comprising an emissive unit attached to the polymer end.
[0053] Figure 2G Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0054] Figure 2H Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0055] Fig.2I Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0056] Figure 2J Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0057] Figure 2K Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0058] Figure 2L Shows an exemplary schematic structure of an emissive polymer comprising common monomer units, emissive monomer units, and functional monomer units (or functional groups).
[0059] FIG. 3A to FIG. 3K Shows non-limiting examples of the schematic structures of an absorbent polymer and an emissive polymer.
[0060] Figure 3A Shows the structure of a binary copolymer comprising an absorbent monomer unit (e.g., a narrow-band absorbent monomer unit) and an emissive monomer unit.
[0061] Figure 3B Shows the structure of a dual-unit alternating copolymer, which comprises an absorbent monomer unit and an emissive monomer unit.
[0062] Figure 3C Shows the structure of a ter-unit alternating copolymer.
[0063] Figure 3D Shows the structure of a dual-unit alternating copolymer having a terminal emissive monomer unit.
[0064] Figure 3E Shows the structure of a dual-unit alternating copolymer having a terminal absorbent monomer unit.
[0065] Figure 3F Shows the structure of a general homopolymer having a terminal emissive monomer unit and a terminal absorbent monomer unit.
[0066] Figure 3G Shows the structure of a ter-copolymer.
[0067] Figure 3H Shows the structure of a tetra-unit alternating copolymer, which comprises an absorbent monomer unit, an emissive monomer unit, and two general monomer units such as general monomer unit 1 (G1) and general monomer unit 2 (G2).
[0068] Fig. 3I Shows the structure of a tetra-unit alternating copolymer, which comprises an absorbent monomer unit, an emissive monomer unit, and two general monomer units such as general monomer unit 1 (G1) and general monomer unit 2 (G2).
[0069] Figure 3J Shows the structure of a ter-copolymer comprising an absorbent unit crosslinked to a side chain.
[0070] Figure 3K Shows the structure of a tetra-copolymer comprising a functionalized general monomer unit (e.g., where F is a functional group, a functional monomer unit, or a functional unit).
[0071] Figure 3L Shows the structure of a tetra-copolymer, which comprises an absorbent monomer unit (A1) present in the polymer backbone and an absorbent unit (A2) crosslinked to the polymer. Both the absorbent monomer unit and the absorbent unit can be energy donors, the general monomer unit can be both an energy donor and an energy acceptor, and the emissive monomer unit can be an energy acceptor.
[0072] Figure 3MShows the structure of a four - unit copolymer, which includes a functionalized general monomer unit (G1), a second general monomer unit (G2) cross - linked with an absorbent unit (A2), an absorbent monomer unit (A1), and an emissive monomer unit (E).
[0073] Figure 3N Shows the structure of a five - unit copolymer, which includes an absorbent monomer unit (A1), a functionalized first general monomer unit (G1) (for example, where F is a functional monomer unit, a functional group, and / or a functional unit), a second general monomer unit (G2) cross - linked with an absorbent unit (A2), a third general monomer unit (G3), and an emissive monomer unit (E).
[0074] Figure 4 Shows non - limiting examples of general monomer units.
[0075] FIG. 5A to FIG. 5E Shows non - limiting examples of the chemical structures of general G1 - type monomer units and G2 - type monomer units for synthesizing polymers (for example, as shown in Figures 1 to 3).
[0076] Figure 5A Shows an exemplary G1 monomer unit.
[0077] Figure 5B Shows an exemplary G2 monomer unit and exemplary derivatives of the G2 monomer unit. For FIG. 5B to FIG. 5E , the derivatives of the G2 monomer unit are labeled as G2' monomer units in the figure. The general G1 - type monomer unit can, for example, be copolymerized with the G2 - type (or G2' - type) monomer unit to obtain a luminescent polymer. For example, any one of the G1 - type monomer unit, G2 - type, or G2' - type monomer unit can also be used alone to copolymerize with an absorbent monomer unit to obtain the polymers shown in Figures 1 to 3. In addition to copolymerization, the absorbent unit and / or the emissive unit can, for example, be attached to the side chain or the end of a polymer formed by any one of the G1 - type monomer unit, G2 - type, or G2' - type monomer units.
[0078] Figure 5C Shows an exemplary G2 monomer unit and exemplary derivatives of the G2 monomer unit.
[0079] Figure 5D Shows an exemplary G2 monomer unit and exemplary derivatives of the G2 monomer unit.
[0080] Figure 5EExemplary G2 monomer units and exemplary derivatives of G2 monomer units are shown. Derivatives of the G2 monomer units are labeled as G2' monomer units in the figure. General G1-type monomer units can, for example, be copolymerized with G2-type (or G2'-type) monomer units to obtain a luminescent polymer. For example, any one of the G1-type monomer units, G2-type or G2'-type monomer units can also be used alone to copolymerize with an absorptive monomer unit to obtain a polymer as shown in FIGS. 1 to 3. In addition to copolymerization, the absorptive unit and / or emissive unit can, for example, be attached to the side chain or end of a polymer formed from any one of the G1-type monomer units, G2-type or G2'-type monomer units.
[0081] Figures 6A to 6Z and Figures 6AA to 6GG Non-limiting examples of different BODIPY derivatives, dyes (e.g., Atto, Alexa, rhodamine, cyanine, coumarin-type dyes), DIBODIPY, pyrene, squaric acid, and their derivatives in absorptive monomer units are shown. Each derivative can be used to synthesize an absorptive homopolymer. Each derivative can also be copolymerized with any general monomer and / or polymer to synthesize an absorptive copolymer. Each derivative can be used as an absorptive unit to crosslink with the side chain of a conventional semiconductor polymer to form an absorptive polymer.
[0082] Fig. 6A Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0083] Figure 6B Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0084] Figure 6C Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0085] Fig.6D Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0086] Fig. 6E Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0087] Fig. 6F Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0088] Figure 6G Non-limiting examples of different BODIPY derivatives as absorptive monomer units are shown.
[0089] Figure 6HIllustrates non - limiting examples of different BODIPY derivatives as absorbent monomer units.
[0090] Fig.6I Illustrates non - limiting examples of different BODIPY derivatives as absorbent monomer units.
[0091] Figure 6J Illustrates non - limiting examples of different BODIPY derivatives as absorbent monomer units.
[0092] Figure 6K Illustrates non - limiting examples of different BODIPY derivatives as absorbent monomer units.
[0093] Figure 6L Illustrates non - limiting examples of different BODIPY derivatives as absorbent monomer units.
[0094] Figure 6M Illustrates non - limiting examples of dye - functionalized monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent dye monomer units. The dyes can include, for example, Atto dye structures, Alexa dye structures, rhodamine dye structures, or coumarin dye structures.
[0095] Figure 6N Illustrates non - limiting examples of cyanine - functionalized monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent cyanine monomer units.
[0096] Fig.6O Illustrates non - limiting examples of cyanine - functionalized monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent cyanine monomer units.
[0097] Figure 6P Illustrates non - limiting examples of DIBODIPY - containing monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent DIBODIPY monomer units.
[0098] Figure 6Q Illustrates non - limiting examples of absorbent monomer units containing DIBODIPY, and an exemplary synthesis of a polymer containing absorbent DIBODIPY monomer units.
[0099] Figure 6R Illustrates non - limiting examples of polymers including DIBODIPY - containing monomers, and an exemplary synthesis of a polymer containing absorbent DIBODIPY monomer units, where the DIBODIPY - containing monomer can be used as an absorbent monomer unit and a general monomer unit.
[0100] Figure 6SShows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0101] Figure 6T Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0102] Figure 6U Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0103] Figure 6V Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0104] Figure 6W Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0105] Figure 6X Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0106] Figure 6Y Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0107] Figure 6Z Shows non - limiting examples of polymers comprising BODIPY - containing absorbent monomer units and general monomer units.
[0108] Figure 6AA Shows non - limiting examples of pyrene - containing monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0109] Figure 6BB Shows non - limiting examples of pyrene - containing monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0110] Figure 6CC Shows non - limiting examples of pyrene - containing monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0111] Figure 6DD Shows non - limiting examples of pyrene - containing monomers that can be used as absorbent monomer units, and an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0112] Figure 6EEShows non-limiting examples of pyrene-containing monomers that can be used as absorbent monomer units, as well as an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0113] Figure 6FF Shows non-limiting examples of squaric acid-containing monomers that can be used as absorbent monomer units, as well as an exemplary synthesis of a polymer containing absorbent squaric acid monomer units.
[0114] Figure 6GG Shows non-limiting examples of pyrene-containing monomers that can be used as absorbent monomer units, as well as an exemplary synthesis of a polymer containing absorbent pyrene monomer units.
[0115] Fig. 7A Shows a non-limiting list of polymers including metal complexes and their derivatives. For 7A to 7C , different Pt complexes are used as absorbent and / or emissive monomer units in the listed polymers, and other metal complexes can also be used. Each metal complex can be copolymerized with any general polymer to synthesize absorbent and / or emissive copolymers. Each metal complex can be used as an absorbent and / or emissive unit to crosslink with the side chains of conventional semiconductor polymers to form polymers.
[0116] Figure 7B Shows a non-limiting list of polymers including metal complexes and their derivatives.
[0117] Figure 7C Shows a non-limiting list of polymers including metal complexes and their derivatives.
[0118] Figure 8 Shows a non-limiting list of polymers including porphyrins, metalloporphyrins and their derivatives as monomer units, as well as an exemplary synthesis of a polymer containing porphyrin repeating units. Each porphyrin derivative can be copolymerized with any general polymer to synthesize absorbent and / or emissive copolymers. Each porphyrin derivative can be used as an absorbent and / or emissive unit to crosslink with the side chains of conventional semiconductor polymers.
[0119] 9A to 9D Shows an example of how to determine the maximum absorbance of a polymer or nanoparticle.
[0120] Fig. 9A Shows an absorption peak with a perfect baseline.
[0121] Fig. 9B Shows an absorption peak where a corrected baseline is used to calculate the maximum absorbance.
[0122] Fig. 9C Shows two absorption peaks where the maximum absorbance is calculated based on the main absorption peak, and the two absorption peaks can be distinguished from each other.
[0123] Fig.9D Two absorption peaks are shown, where the maximum absorbance is calculated based on the main absorption peak, and the two absorption peaks are distinguishable from each other, as shown using the corrected baseline.
[0124] FIG. 10A to FIG. 10C The multi-step synthesis of a series of monomers and the synthesis of the narrow-band absorbing polymer P2 are shown.
[0125] Fig. 10A The synthesis of benzoxazole-based monomer 1 is shown.
[0126] Fig. 10B The synthesis of BODIPY-based monomer 2 is shown.
[0127] Fig. 10C The polymerization reaction to form polymer P2 is shown.
[0128] FIG. 11A to FIG. 11C The multi-step synthesis of monomers and the narrow-band absorbing polymer P7 are shown.
[0129] Fig.11A The synthesis of BODIPY-based monomer 5 is shown.
[0130] Fig. 11B The synthesis of fluorene-based monomer 6 is shown.
[0131] Fig. 11C The polymerization reaction to form polymer P7 is shown.
[0132] Fig.12 A schematic diagram of BODIPY-based narrow-absorbing polymer dots and Pdot bioconjugates for specific cell targeting is shown.
[0133] Fig.13 A schematic diagram of a non-limiting example of forming Pdot using a general absorbent polymer and Eu complex is shown.
[0134] FIG. 14A to FIG. 14D The photophysical properties of the polymer (polymer P1) are shown.
[0135] Fig.14A The absorbance of the polymer dissolved in THF is shown.
[0136] Fig. 14B The emission of the polymer in THF is shown.
[0137] Fig. 14C The absorbance of the polymer in its Pdot state is shown.
[0138] Fig.14D The emission of the polymer in its Pdot state is shown.
[0139] FIG. 15A to FIG. 15D Shows the photophysical properties of the polymer (Polymer P2).
[0140] Fig.15A Shows the absorbance of the polymer dissolved in THF.
[0141] Fig. 15B Shows the emission of the polymer in THF.
[0142] Fig. 15C Shows the absorbance of the polymer in its Pdot state.
[0143] Fig.15D Shows the emission of the polymer in its Pdot state.
[0144] FIG. 16A to FIG. 16D Shows the photophysical properties of the polymer (Polymer P3).
[0145] Fig.16A Shows the absorbance of the polymer dissolved in THF.
[0146] Fig. 16B Shows the emission of the polymer in THF.
[0147] Fig. 16C Shows the absorbance of the polymer in its Pdot state.
[0148] Fig.16D Shows the emission of the polymer in its Pdot state.
[0149] 17A to 17D Shows the photophysical properties of the polymer (Polymer P4).
[0150] Fig.17A Shows the absorbance of the polymer dissolved in THF.
[0151] Fig. 17B Shows the emission of the polymer in THF.
[0152] Fig. 17C Shows the absorbance of the polymer in its Pdot state.
[0153] Fig.17D Shows the emission of the polymer in its Pdot state.
[0154] 18A to 18D Shows the photophysical properties of the polymer (Polymer P5).
[0155] Fig.18A Shows the absorbance of the polymer dissolved in THF.
[0156] Fig.18B Shows the emission of the polymer in THF.
[0157] Fig. 18C Shows the absorbance of the polymer in its Pdot state.
[0158] Fig.18D Shows the emission of the polymer in its Pdot state.
[0159] FIG. 19A to FIG. 19B Shows the photophysical properties of the polymer (Polymer P6).
[0160] Fig.19A Shows the absorbance of the polymer dissolved in THF.
[0161] Fig.19B Shows the emission of the polymer in THF.
[0162] Fig.19C Shows the absorbance of the polymer in its Pdot state.
[0163] Fig.19D Shows the emission of the polymer in its Pdot state.
[0164] FIG. 20A to FIG. 20D Shows the photophysical properties of the polymer (Polymer P7).
[0165] Fig. 20A Shows the absorbance of the polymer dissolved in THF.
[0166] Fig. 20B Shows the emission of the polymer in THF.
[0167] Fig. 20C Shows the absorbance of the polymer in its Pdot state.
[0168] Fig.20D Shows the emission of the polymer in its Pdot state.
[0169] FIG. 21A to FIG. 21B Shows the photophysical properties of the polymer dots comprising 80 wt% of Polymer P8 and 20 wt% of Polymer P9.
[0170] Fig.21A Shows the absorbance of the polymer in its Pdot state.
[0171] Fig.21B Shows the emission of the polymer in its Pdot state.
[0172] Fig. 22Shows a comparison of Pdot of PFGBDP Pdot, PFDHTBT-BDP720 Pdot, and Pdot of a blend including both PFGBDP and PFDHTBT-BDP720.
[0173] FIG. 23A to FIG. 23C Shows the spectral characteristics of nanoparticles including polymer P8, polymer P9, and blend polymer.
[0174] Fig.23A Shows 0.005 g L -1 Absolute absorbance (Abs; solid line) and fluorescence (FL; dashed line) of PFGBDP Pdot, PFDHTBT-BDP720 Pdot, and blended Pdot.
[0175] Fig. 23B Shows the normalized absorption and photoluminescence spectra of PFGBDP and PFFDHTBT Pdot and BDP720 dye in the nanoparticle state.
[0176] Fig.23C Shows the energy levels of GBDP monomer, GBDP H-dimer, PFDHTBT, and BDP720 in the Pdot state, and the cascade energy transfer between them. Detailed Description
[0177] It is desirable to obtain polymer dots (Pdot) with narrow-band absorption, but this may be difficult to achieve. Narrow-band absorbing nanoparticles with high quantum yield are beneficial, but this may be difficult due to fluorescence self-quenching of monomer units or emitting units in the condensed polymer state of polymer nanoparticles. When an improved quantum yield or narrow-band absorption from the nanoparticles is achieved, it may be at the expense of a reduced absorption cross-section or reduced brightness. The present disclosure proposes an enhanced network of absorptive monomer units and / or absorptive units and emissive monomer units and / or emissive units and / or general monomer units that can improve energy transfer, which can help synchronously increase the quantum yield and brightness while achieving narrow-band absorption. In some embodiments, the general monomer units provide other functions, such as providing hydrophilicity or amphiphilicity, or reactive functional groups. For example, the general monomer units can include energy transfer monomer units and / or can include functional monomer units.
[0178] The brightness or narrow-band absorption of polymer nanoparticles depends in part on the structural aspects within the polymer nanoparticles. For example, a polymer dissolved in an organic solution may have a high quantum yield, but the same polymer may have a significantly reduced quantum yield after collapsing into the nanoparticle state. Therefore, it is beneficial to introduce additional polymers or monomer units to provide structure and / or energy transfer carriers in the polymer nanoparticles.
[0179] Embodiments of the present application relate to a new class of luminescent nanoparticles called narrow-band absorbing polymer dots and their biomolecular conjugates for use in a variety of applications, including but not limited to flow cytometry, fluorescence-activated sorting, immunofluorescence, immunohistochemistry, fluorescence multiplexing, single molecule imaging, single particle tracking, protein folding, protein rotational dynamics, DNA and gene analysis, protein analysis, metabolite analysis, lipid analysis, FRET-based sensors, high-throughput screening, cell detection, bacterial detection, viral detection, biomarker detection, cell imaging, in vivo imaging, bioorthogonal labeling, click reactions, fluorescence-based biological assays (such as immunoassays and enzyme-based assays), and various fluorescence techniques in biological assays and measurements.
[0180] Although not limited to any particular theory or concept, the present disclosure is at least partially based on the fact that semiconductor polymer-based luminescent Pdots typically have a broad absorption spectrum with an absorption peak width greater than 200 nm at 10% (or in some cases, at 15%) of the absorbance maximum. This broadband absorption can be a significant drawback for fluorescence techniques in biology and fluorescence multiplexing. To overcome the challenges of current Pdots, the present disclosure provides compositions and methods for obtaining next-generation Pdots with narrow-band absorption. In addition, the present disclosure provides compositions and methods that allow for bioconjugation to polymer dots while still maintaining their narrow-band absorption.
[0181] In some aspects, the properties of narrow-band absorbing polymers and polymer dots can depend on the polymer structure. Thus, the polymer backbone, side chains, end units, and substituents can be varied to obtain specific properties. In some embodiments, the optical properties of narrow-band polymers and polymer dots can be tuned by altering the structure of the polymer backbone. For example, absorption and fluorescence emission can be redshifted by increasing the conjugation length of the polymer backbone, or absorption and fluorescence emission can be blueshifted by decreasing the conjugation length of the polymer backbone. For example, monomer units containing benzothiadiazole (BT) or BT derivatives can increase the photostability of certain types of resulting polymer dots compared to polymers that do not have BT or BT derivatives in their polymer backbones.
[0182] In some embodiments, the optical properties of narrow-band absorbing polymers and polymer dots can be modified by changing the side chains, end units, and substituents. For example, the absorption band or fluorescence emission wavelength can be tuned by attaching chromophoric units to the side chains and / or ends. The absorption bandwidth, absorption peak, emission bandwidth, fluorescence quantum yield, fluorescence lifetime, photostability, and other properties can also be modified by changing the polymer side chains and / or end units in addition to the polymer backbone. In another example, derivatives of anti-fading agents such as butylated hydroxytoluene, trolox, carotenoids, ascorbic acid, reduced glutathione, propyl gallate, stearic acid propionate, hydroxyquinone, p-phenylenediamine, triphenylamine, β-mercaptoethanol, trans-stilbene, imidazole, Mowiol, or combinations thereof, or any other combination of anti-fading agents known in the art, can increase the quantum yield, photostability, or both through the attachment and presence of the side chains, end units, backbone, and / or substituents to the polymer. These anti-fading agents generally act as antioxidants to reduce oxygen, and / or act as scavengers of reactive oxygen species, and / or act to inhibit the photo-generated hole polarons within the polymer dots. In a preferred embodiment, the anti-fading agent is hydrophobic in nature so as not to adversely affect the packing and / or colloidal stability of the polymer dots. In some embodiments, the absorption peak, absorption bandwidth, emission peak, emission bandwidth, fluorescence quantum yield, fluorescence lifetime, photostability, and other properties of narrow-band absorbing polymers and polymer dots can also be modified by substituents on the polymer. For example, the degree of electron-donating or electron-withdrawing ability of the substituents can be used to tune the optical properties. For example, the two-photon absorption cross-section can be increased by modular structures such as donor-π-donor or donor-acceptor-donor units.
[0183] In some embodiments, the colloidal properties of polymer dots can be improved by changing the polymer backbone, side chains, end units, and substituents. In some embodiments, the polymer dots can include hydrophobic functional groups in the side chains, end units, and / or substituents. In other embodiments, the polymer dots can include hydrophilic functional groups in the side chains, end units, and / or substituents. The length, size, and nature of the hydrophobic / hydrophilic side chains can modify the chain-chain interactions, control the packing of the polymer, and affect the colloidal stability and size of the polymer dots. The length, size, and nature of the hydrophobic / hydrophilic side chains can also affect the absorption bandwidth, absorption peak, emission peak, emission bandwidth, fluorescence quantum yield, fluorescence lifetime, photostability, and other properties of narrow-band absorbing polymers and polymer dots. For example, a large number of very hydrophilic functional groups can reduce the brightness of the polymer dots, and / or broaden the emission spectrum, and / or adversely affect their colloidal stability and non-specific binding properties.
[0184] definition
[0185] As used herein, "monomeric unit" refers to a group of atoms of a molecule derived from a given monomer, including the constituent units of a polymer or macromolecule.
[0186] As used herein, a monomer refers to a molecule that can undergo polymerization to contribute a constituent unit to the basic structure of a macromolecule. As used herein, when a monomer forms part of a polymer chain, it should be understood that the monomer refers to the monomeric unit.
[0187] As used herein, the term "constituent unit" of a polymer refers to an atom or group of atoms in the polymer, including a part of the chain and its side chain atoms or groups (if any). The constituent unit may refer to a repeating unit. The constituent unit may also refer to the end group on the polymer chain. For example, the constituent unit of polyethylene glycol may be -CH2CH2O- corresponding to the repeating unit or -CH2CH2OH corresponding to the end group.
[0188] As used herein, the term "repeating unit" corresponds to the smallest constituent unit whose repetition constitutes a regular macromolecule (or oligomer molecule or block).
[0189] As used herein, the term "end group" refers to a constituent unit located at the end of a polymer that has only one connection to the polymer chain. For example, once the monomer has polymerized, the end group can be derived from the monomeric unit at the end of the polymer. As another example, the end group can be part of a chain transfer agent or initiator used to synthesize the polymer.
[0190] As used herein, the term "end" of a polymer refers to the constituent unit of the polymer located at the end of the polymer backbone.
[0191] As used herein, the term "biodegradable" refers to the process of degrading a material through hydrolysis and / or catalytic degradation processes, such as enzyme-mediated hydrolysis and / or oxidation. For example, a polymer side chain can be cleaved from the polymer backbone through hydrolysis or a catalytic process (e.g., enzyme-mediated hydrolysis and / or oxidation).
[0192] "Biocompatibility" refers to a property of a molecule characterized in that the molecule or its in vivo degradation products do not cause harm to living tissue, or cause at least minimal and / or reparable harm to living tissue; and / or do not cause an immune response in living tissue, or cause an immune response in living tissue at least minimally and controllably. As used herein, "physiologically acceptable" can be used interchangeably with biocompatibility.
[0193] As used herein, the term "hydrophobic" refers to a portion that has a significant non-polar surface area and is not attracted to water. This phase separation can be observed by combining dynamic light scattering and aqueous NMR measurements. Hydrophobic constituent units tend to be non-polar under aqueous conditions. Examples of hydrophobic portions include alkyl groups, aryl groups, etc.
[0194] As used herein, the term "hydrophilic" refers to a moiety that is attracted to water and tends to be water-soluble. The hydrophilic moiety may be miscible with water. The hydrophilic building units can be polar and / or ionizable under aqueous conditions. The hydrophilic building units can be ionizable under aqueous conditions and / or can contain polar groups such as amines, hydroxyls, or ethylene glycol residues. Examples of hydrophilic moieties include carboxyl groups, amino groups, hydroxyl groups, etc.
[0195] As used herein, the term "cationic" refers to a moiety that is positively charged or ionizable to a positively charged moiety under physiological conditions. Examples of cationic moieties include, for example, amino groups, ammonium, pyridinium, imino, sulfonium, quaternary phosphonium groups, etc.
[0196] As used herein, the term "anionic" refers to a functional group that is negatively charged or ionizable to a negatively charged moiety under physiological conditions. Examples of anionic groups include carboxylate, sulfate, sulfonate, phosphate, etc.
[0197] As used herein, the term "chromogenic polymer nanoparticles" or "chromogenic polymer dots" refers to a structure that includes one or more polymers (e.g., chromogenic polymers, semiconductor polymers) that have been formed into stable submicron-sized particles. The chromogenic polymer nanoparticles or chromogenic polymer dots of the present disclosure can, for example, include a single polymer or can, for example, be chemically crosslinked and / or physically blended polymers. "Polymer dots" and "Pdot" can be used interchangeably to refer to "nanoparticles" or "polymer dots". In certain embodiments, the polymer nanoparticles include one or more chromogenic polymers (e.g., semiconductor polymers) and can be referred to as chromogenic polymer dots, chromogenic polymer nanoparticles, or chromogenic nanoparticles. The polymer dots provided herein can be formed by any method known in the art, including but not limited to methods that rely on precipitation, methods that rely on the formation of emulsions (e.g., miniemulsions or microemulsions), and methods that rely on condensation. The Pdot described herein is different from and distinguishable from nanoparticles formed from aggregates of polyelectrolytes. Unless otherwise specified, "polymer dots", "Pdot", or "nanoparticles" herein refers to narrow-band absorbing polymer dots.
[0198] As used herein, "polymer" refers to a molecule composed of at least two repeating structural units, typically connected by covalent chemical bonds. The repeating structural units can be of one type of monomer unit, and the resulting polymer is a homopolymer. In some embodiments, the polymer can include two different types of monomer units, or three different types of monomer units, or more types of monomer units to produce a heteropolymer. One of ordinary skill in the art will understand that different types of monomer units can be distributed along the polymer chain in a variety of ways. For example, three different types of monomer units can be randomly distributed along the polymer. Similarly, it will be understood that the distribution of monomer units along the polymer can be represented in different ways. The number of repeating structural units (e.g., monomer units) along the length of the polymer can be represented by "n". In some embodiments, n can be in the range of, for example, at least 2, at least 100, at least 500, at least 1000, at least 5000, or at least 10,000, or at least 100,000, or higher. In certain embodiments, n can be from 2 to 10,000, from 20 to 10,000, from 20 to 500, from 50 to 300, from 100 to 1000, or from 500 to 10,000.
[0199] Polymers generally have an extended molecular structure, including a backbone that may optionally contain side groups. The polymers provided herein can include, but are not limited to, linear polymers and branched polymers such as star polymers, comb polymers, brush polymers, ladder polymers, and dendrimers. As further described herein, the polymers can include semiconductor polymers well known in the art.
[0200] As used herein, the term "chromogenic polymer" is a polymer in which at least a portion of the polymer includes chromogenic units. The term "chromophore" has its ordinary meaning in the art. A chromophore absorbs light of specific wavelengths from the UV to the near-infrared region and may or may not be emissive. A chromogenic polymer can be, for example, a "conjugated polymer". The term "conjugated polymer" is well recognized in the art. Electrons, holes, or electronic energy can be conducted along the conjugated structure. In some embodiments, a majority of the polymer backbone can be conjugated. In some embodiments, the entire polymer backbone can be conjugated. In some embodiments, the polymer can include a conjugated structure in its side chains or at its termini. In some embodiments, a conjugated polymer can have conductive properties, e.g., the polymer can conduct electricity. In some embodiments, a conjugated polymer can have semiconductor properties and is referred to as a "semiconductor polymer", e.g., the polymer can exhibit a direct bandgap, resulting in efficient absorption or emission at the band edges.
[0201] The "chromogenic unit" in the present disclosure includes, but is not limited to, units having a structure with delocalized π electrons, units of small organic dye molecules, and / or units of metal complexes. Examples of chromogenic polymers may include: polymers including units having a structure with delocalized π electrons, such as semiconductor polymers; polymers including units of small organic dye molecules; polymers including units of metal complexes; and polymers including units of any combination thereof. The chromogenic unit may be incorporated into the polymer backbone. The chromogenic unit may also be covalently linked to the side chain or end unit of the polymer.
[0202] The "emission spectrum" of a polymer dot is defined as the spectrum of the wavelengths (or frequencies) of electromagnetic radiation emitted by the polymer dot when the polymer dot is excited to a higher energy state and then returns to a lower energy state. The width of the emission spectrum can be characterized by its full width at half maximum (FWHM). The FWHM of the emission spectrum is defined as the distance between the points on the emission curve where the emission intensity reaches half of its maximum value. The emission characteristics of the polymer dot can also be characterized by the fluorescence quantum yield and the fluorescence lifetime. The fluorescence quantum yield gives the efficiency of the fluorescence process. It is defined as the ratio of the number of photons emitted by Pdot to the number of photons absorbed. The fluorescence lifetime is defined as the average time that the polymer dot stays in its excited state before emitting a photon. All of the above-defined parameters, such as the emission spectrum, FWHM, fluorescence quantum yield, and fluorescence lifetime, can be measured experimentally. In the present disclosure, these parameters can be specifically used to characterize the Pdot with narrowband emission.
[0203] The "absorption spectrum" of a polymer dot is defined as the spectrum of the wavelengths (or frequencies) of electromagnetic radiation absorbed by the polymer dot, which excites the polymer dot to a higher energy state before it returns to a lower energy state. In some embodiments, the energy state corresponding to the absorption spectrum is an electronic transition.
[0204] As used herein, the term "alkyl" refers to a straight-chain or branched-chain saturated aliphatic group having the indicated number of carbon atoms. For example, C1-C6 alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and the like. Other alkyls include, but are not limited to, heptyl, octyl, nonyl, decyl, and the like. An alkyl can include any number of carbons, such as 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 2-3, 2-4, 2-5, 2-6, 3-4, 3-5, 3-6, 4-5, 4-6, and 5-6. As non-limiting examples, an alkyl can include 100-1, 50-40, 50-30, 50-20, 50-10, 50-1, 40-30, 40-20, 40-10, 40-1, 30-25, 30-20, 30-15, 30-10, 30-5, 30-1, 25-20, 25-15, 25-10, 25-5, 25-1, 20-15, 20-10, 20-5, 20-1, 15-10, 15-5, 15-1, 10-5, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 2-3, 2-4, 2-5, 2-6, 3-4, 3-5, 3-6, 4-5, 4-6, or 5-6 carbon atoms. An alkyl is generally monovalent, but can be divalent, for example when the alkyl links two moieties together. As used herein, the term "heteroalkyl" refers to a straight-chain or branched-chain saturated aliphatic group of carbon atoms in which at least one carbon atom is replaced by a heteroatom such as N, O, or S. Additional heteroatoms can also be used, including, but not limited to, B, Al, Si, and P. An alkyl can be halogenated, where at least one carbon atom is covalently linked to a halogen such as F, Cl, Br, or I.
[0205] The term "lower", as referred to above and hereinafter in connection with organic groups or compounds, respectively defines a compound or group, which can be branched or unbranched, having at most and including 7, preferably at most and including 4, and (as unbranched) one or two carbon atoms.
[0206] As used herein, the term "alkylene" refers to an alkyl as defined above that links at least two other groups (i.e., a divalent hydrocarbon group). The two moieties attached to the alkylene can be attached to the same atom or different atoms of the alkylene. For example, a straight-chain alkylene can be a divalent group of -(CH2) n where n is 1, 2, 3, 4, 5, or 6. Alkylenes include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, pentylene, and hexylene.
[0207] The groups described herein can be substituted or unsubstituted. The substituents of alkyl and heteroalkyl (including those groups commonly referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl and heterocycloalkenyl) can be various groups such as alkyl, aryl, cyano (CN), amino, sulfide, aldehyde, ester, ether, acid, hydroxyl or halide. The substituents can be reactive groups such as, but not limited to, fluorine, chlorine, bromine, iodine, hydroxyl or amino. Suitable substituents can be selected from, for example: -OR', =O, =NR', =N-OR', -NR'R", -SR', -halogen, -SiR'R"R"', -OC(O)R', -C(O)R', -CO2R', -CONR'R", -OC(O)NR'R", -NR"C(O)R', -NR'-C(O)NR"R"', -NR"C(O)2R', -NH-C(NH2)=NH, -NR'C(NH2)=NH, -NH-C(NH2)=NR', -S(O)R', -S(O)2R', -S(O)2NR'R", -CN and -NO2, the number of which is zero to (2m'+1), where m' is the total number of carbon atoms in such groups. R', R" and R"' each independently refer to hydrogen, unsubstituted (C1-C8) alkyl and heteroalkyl, unsubstituted aryl, alkoxy or thioalkoxy, or aryl-(C1-C4)alkyl. When R' and R" are attached to the same nitrogen atom, they can combine with the nitrogen atom to form a 5-, 6- or 7-membered ring. For example, -NR'R" is intended to include 1-pyrrolidinyl and 4-morpholinyl. From the above discussion of substituents, those skilled in the art will understand that the term "alkyl" is intended to include groups such as haloalkyl (e.g., -CF3 and -CH2CF3) and acyl (e.g., -C(O)CH3, -C(O)CF3, -C(O)CH2OCH3, etc.).
[0208] As used herein, the term "alkoxy" refers to an alkyl group having an oxygen atom that attaches the alkoxy group to a point of attachment or to two carbons of the alkoxy group. Alkoxy groups include, for example, methoxy, ethoxy, propoxy, iso-propoxy, butoxy, 2-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, ethers, polyethers (e.g., polyethylene glycol (PEG)), and the like. The alkoxy group can be further substituted with various substituents described herein. For example, the alkoxy group can be substituted with a halogen to form a "halo-alkoxy". As a non-limiting example, the alkoxy group can include from 100 to 1, 50 to 40, 50 to 30, 50 to 20, 50 to 10, 50 to 1, 40 to 30, 40 to 20, 40 to 10, 40 to 1, 30 to 25, 30 to 20, 30 to 15, 30 to 10, 30 to 5, 30 to 1, 25 to 20, 25 to 15, 25 to 10, 25 to 5, 25 to 1, 20 to 15, 20 to 10, 20 to 5, 20 to 1, 15 to 10, 15 to 5, 15 to 1, 10 to 5, 1 to 2, 1 to 3, 1 to 4, 1 to 5, 1 to 6, 1 to 7, 1 to 8, 1 to 9, 1 to 10, 2 to 3, 2 to 4, 2 to 5, 2 to 6, 3 to 4, 3 to 5, 3 to 6, 4 to 5, 4 to 6, or 5 to 6 carbon atoms.
[0209] As used herein, the term "alkenyl" refers to a straight-chain or branched-chain hydrocarbon of 2 to 6 carbon atoms having at least one double bond. Examples of alkenyl groups include, but are not limited to, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, butadienyl, 1-pentenyl, 2-pentenyl, isopentenyl, 1,3-pentadienyl, 1,4-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,5-hexadienyl, 2,4-hexadienyl, or 1,3,5-hexatriene.
[0210] As used herein, the term "alkenylene" refers to an alkenyl group as defined above that connects at least two other groups (i.e., a divalent hydrocarbon group). The two moieties attached to the alkenylene group can be attached to the same atom or different atoms of the alkenylene group. Alkenylene groups include, but are not limited to, vinylene, propenylene, isopropenylene, butenylene, isobutenylene, sec-butenylene, pentenylene, and hexenylene.
[0211] As used herein, the term "alkynyl" refers to a straight-chain or branched-chain hydrocarbon having from 2 to 6 carbon atoms and having at least one triple bond. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, 1-butynyl, 2-butynyl, isobutynyl, sec-butynyl, butadiynyl, 1-pentynyl, 2-pentynyl, isopentynyl, 1,3-pentadiynyl, 1,4-pentadiynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 1,3-hexadiynyl, 1,4-hexadiynyl, 1,5-hexadiynyl, 2,4-hexadiynyl or 1,3,5-hexatriynyl.
[0212] As used herein, the term "alkynylene" refers to an alkynyl group as defined above that links at least two other groups (i.e., a divalent hydrocarbon group). The two moieties attached to the alkynylene group may be attached to the same atom or different atoms of the alkynylene group. Alkynylene includes, but is not limited to, ethynylene, propynylene, isopropynylene, butynylene, sec-butynylene, pentynylene and hexynylene.
[0213] As used herein, the term "alkylamine" refers to an alkyl group having one or more amino groups as defined herein. The amino group may be a primary, secondary or tertiary amino group. The alkylamine may be further substituted with a hydroxyl group. Alkylamines include, but are not limited to, ethylamine, propylamine, isopropylamine, ethylenediamine and ethanolamine. The amino group may connect the alkylamine to the point of attachment to the remainder of the compound, may be located at the ω-position of the alkyl group, or may connect together at least two carbon atoms of the alkyl group.
[0214] As used herein, the term "halogen" or "halide" refers to fluorine, chlorine, bromine and iodine. As used herein, the term "haloalkyl" refers to an alkyl group as defined above in which some or all of the hydrogen atoms are replaced by halogen atoms. The halogen (halo) preferably represents chlorine or fluorine, but may also be bromine or iodine. As used herein, the term "halo-alkoxy" refers to an alkoxy group having at least one halogen. A halo-alkoxy is defined as an alkoxy group in which some or all of the hydrogen atoms are replaced by halogen atoms. The alkoxy group may be substituted with 1, 2, 3 or more halogens. When all of the hydrogens are replaced by halogen (e.g., by fluorine), these compounds are fully-substituted, e.g., perfluorinated. Halo-alkoxy groups include, but are not limited to, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, etc.
[0215] As used herein, the term "cycloalkyl" refers to a saturated or partially unsaturated monocyclic, fused bicyclic or bridged polycyclic assembly having from 3 to 12 ring atoms or the indicated number of atoms. Monocyclics include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. Bicyclics and polycyclics include, for example, norbornane, decalin and adamantane. For example, C 3-8 Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and norbornane.
[0216] As used herein, the term "subcycloalkyl" refers to a cycloalkyl group that connects at least two other groups (i.e., a divalent hydrocarbon group) as defined above. The two moieties attached to the subcycloalkyl may be attached to the same atom or different atoms of the subcycloalkyl. Subcycloalkyl includes, but is not limited to, subcyclopropyl, subcyclobutyl, subcyclopentyl, subcyclohexyl, and subcyclooctyl.
[0217] As used herein, the term "heterocycloalkyl" refers to a ring system having from 3 to about 20 ring members and from 1 to about 5 heteroatoms such as N, O, and S. Additional heteroatoms may also be used, including, but not limited to, B, Al, Si, and P. The heteroatoms may also be oxidized, such as, but not limited to, -S(O)- and -S(O)2-.
[0218] As used herein, the term "heterocycloalkylene" refers to a heterocycloalkyl group that connects at least two other groups as defined above. The two moieties attached to the heterocycloalkylene may be attached to the same atom or different atoms of the heterocycloalkylene.
[0219] As used herein, the term "aryl" refers to a monocyclic or fused bicyclic, tricyclic or larger aryl ring assembly containing 6 to 16 ring carbon atoms. For example, aryl may be phenyl, benzyl, azulyl or naphthyl. "Arylene" refers to a divalent group derived from aryl. The aryl may be mono-substituted, di-substituted or tri-substituted by one, two or three groups selected from alkyl, alkoxy, aryl, hydroxy, halogen, cyano, amino, amino-alkyl, trifluoromethyl, alkylenedioxy and oxy-C2-C3-alkylene; all of these groups are optionally further substituted, for example as defined above; or 1-naphthyl or 2-naphthyl; or 1- or 2-phenanthryl. Alkylenedioxy is a divalent substituent attached to two adjacent carbon atoms of a phenyl group, for example, methylenedioxy or ethylenedioxy. Oxy-C2-C3-alkylene is also a divalent substituent attached to two adjacent carbon atoms of a phenyl group, for example, oxyethylene or oxypropylene. An example of oxy-C2-C3-alkylene-phenyl is 2,3-dihydrobenzofuran-5-yl.
[0220] Aryl may include, but is not limited to, naphthyl, phenyl or phenyl mono-substituted or di-substituted by alkoxy, phenyl, halogen, alkyl or trifluoromethyl, phenyl or phenyl mono-substituted or di-substituted by alkoxy, halogen or trifluoromethyl, especially phenyl.
[0221] As used herein, the term "arylene" refers to an aryl group that connects at least two other groups as defined above. The two moieties attached to the arylene are attached to different atoms of the arylene. Arylene includes, but is not limited to, phenylene.
[0222] As used herein, the term "alkoxy-aryl" or "aryloxy" refers to an aryl group as defined above, wherein one of the moieties attached to the aryl group is attached through an oxygen atom. Alkoxy-aryl includes, but is not limited to, phenoxy (C6H5O-). The present disclosure also includes alkoxy-heteroaryl or heteroaryloxy.
[0223] As used herein, the term "heteroaryl" refers to a monocyclic or fused bicyclic or tricyclic aromatic ring assembly containing 5 to 16 ring atoms, wherein 1 to 4 ring atoms are heteroatoms each independently being N, O or S. For example, heteroaryl includes pyridyl, indolyl, indazolyl, quinoxalinyl, quinolinyl, isoquinolinyl, benzothienyl, benzofuranyl, furanyl, pyrrolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, thienyl, or any other substituted group, especially a group mono-substituted or di-substituted by, for example, alkyl, nitro or halogen. Suitable groups for the present disclosure may also include heteroarylene and heteroarylene-oxy similar to the above-mentioned arylene and arylene-oxy.
[0224] Similarly, the aryl and heteroaryl groups described herein may be substituted or unsubstituted. The substituents of the aryl and heteroaryl groups vary, such as alkyl, aryl, CN, amino, sulfide, aldehyde, ester, ether, acid, hydroxy or halide. The substituents may be reactive groups, such as but not limited to chlorine, bromine, iodine, hydroxy or amino. The substituents are selected from: -halogen, -OR', -OC(O)R', -NR'R", -SR', -R', -CN, -NO2, -CO2R', -CONR'R", -C(O)R', -OC(O)NR'R", -NR"C(O)R', -NR"C(O)2R', -NR'-C(O)NR"R"', -NH-C(NH2)=NH, -NR'C(NH2)=NH, -NH-C(NH2)=NR', -S(O)R', -S(O)2R', -S(O)2NR'R", -N3, -CH(Ph)2, in a number ranging from zero to the total number of open valences on the aromatic ring system; and wherein R', R" and R"' are independently selected from hydrogen, (C1-C8) alkyl and heteroalkyl, unsubstituted aryl and heteroaryl, (unsubstituted aryl)-(C1-C4) alkyl and (unsubstituted aryl)oxy-(C1-C4) alkyl.
[0225] As used herein, the term "alkyl-aryl" refers to a group having an alkyl component and an aryl component, wherein the alkyl component connects the aryl component to the point of attachment. The alkyl component is as defined above, except that the alkyl component is at least divalent in order to connect to the aryl component and the point of attachment. In some cases, the alkyl component may be absent. The aryl component is as defined above. Examples of alkyl-aryl include, but are not limited to, benzyl. The present disclosure also includes alkyl-heteroaryl.
[0226] As used herein, the term "alkenyl-aryl" refers to a group having both an alkenyl moiety and an aryl moiety, wherein the alkenyl moiety connects the aryl moiety to a point of attachment. The alkenyl moiety is defined as above, except that the alkenyl moiety is at least divalent so as to connect to the aryl moiety and the point of attachment. The aryl moiety is defined as above. Examples of alkenyl-aryl include vinyl-phenyl and the like. The present disclosure also includes alkenyl-heteroaryl.
[0227] As used herein, the term "alkynyl-aryl" refers to a group having both an alkynyl moiety and an aryl moiety, wherein the alkynyl moiety connects the aryl moiety to a point of attachment. The alkynyl moiety is defined as above, except that the alkynyl moiety is at least divalent so as to connect to the aryl moiety and the point of attachment. The aryl moiety is defined as above. Examples of alkynyl-aryl include ethynyl-phenyl and the like. The present disclosure also includes alkynyl-heteroaryl.
[0228] As will be understood by one of ordinary skill in the art, the various chemical terms defined herein can be used to describe the chemical structures of the polymers and monomer units of the present disclosure. For example, various monomer unit derivatives (e.g., BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof) can include the various chemical substituents and groups described herein. For example, in some embodiments, derivatives of the various monomer units can be substituted with hydrogen, deuterium, alkyl, aralkyl, aryl, alkoxy-aryl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, N-dialkoxyphenyl-4-phenyl, amino, sulfide, aldehyde, ester, ether, acid, and / or hydroxyl.
[0229] The compounds described herein can be asymmetric (e.g., having one or more stereocenters). Unless otherwise indicated, all stereoisomers, such as enantiomers and diastereomers, are meant.
[0230] The compounds of the present disclosure containing asymmetrically substituted carbon atoms can be isolated in optically active form or in racemic form. Methods for how to prepare optically active forms from optically active starting materials are known in the art, such as by resolution of a racemic mixture or by stereoselective synthesis. Many geometric isomers of alkenes, C=N double bonds, etc. can also be present in the compounds described herein, and all such stable isomers are contemplated in the present disclosure. The cis and trans geometric isomers of the compounds of the present disclosure are described and can be isolated as a mixture of isomers or as separated isomer forms.
[0231] The compounds of the present disclosure also include tautomeric forms. Tautomeric forms are caused by the exchange of a single bond with an adjacent double bond and the accompanying migration of a proton. Tautomeric forms include prototropic tautomers, which are isomeric protonated states having the same empirical formula and total charge. Exemplary prototropic tautomers include keto-enol pairs, amide-imidic acid pairs, lactam-lactim pairs, amide-imidic acid pairs, enamine-imine pairs, and cyclic forms, in which the proton can occupy two or more positions in a heterocyclic system, for example, 1H- and 3H-imidazole, 1H-, 2H-, and 4H-1,2,4-triazole, 1H- and 2H-isoindole, and 1H- and 2H-pyrazole. Tautomeric forms can be in equilibrium or sterically locked into one form by appropriate substitution.
[0232] The compounds of the present disclosure may also include all isotopes of atoms that occur in the intermediates or the final compounds. Isotopes include those atoms having the same atomic number but different mass numbers. For example, isotopes of hydrogen include tritium and deuterium.
[0233] In some embodiments, the compounds of the present disclosure and their salts are substantially isolated. "Substantially isolated" means that the compound is at least partially or substantially separated from the environment in which it is formed or detected. Partial separation may include, for example, a composition being enriched in the compound of the present disclosure. Sufficient separation may include a composition containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of the compound of the present disclosure or its salt. Methods for separating the compounds and their salts are conventional in the art.
[0234] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Additionally, the materials, methods, and examples are illustrative only and not restrictive.
[0235] It is readily understood that, as generally described herein and shown in the figures, the aspects of the present disclosure can be arranged, substituted, combined, separated, and designed in various different configurations, all of which are explicitly contemplated herein.
[0236] In addition, the specific arrangements shown in the drawings should not be considered limiting. It should be understood that other embodiments may include more or less each element shown in a given drawing. In addition, some of the elements shown may be combined or omitted. Further still, exemplary embodiments may include elements not shown in the drawings. As used herein, with respect to measurements, "about" means + / - 5%. As used herein, recited ranges include the endpoints such that 0.5 mole % to 99.5 mole % includes both 0.5 mole % and 99.5 mole %.
[0237] Absorption and emission from narrowband absorbing nanoparticles
[0238] In at least one embodiment, the present disclosure provides polymer dots having at least one narrow band absorption (also referred to herein as "narrow absorption bandwidth" and "narrow band absorbance"). The absorption width at 10% (or in some embodiments, at 15%) of the absorbance maximum of the narrow band absorption can be less than 150 nm.
[0239] In some embodiments, the present disclosure provides polymer dots comprising a polymer that includes absorbent monomer units and emissive monomer units. An "absorbent monomer unit" is a unit that absorbs electromagnetic radiation that can change the state of the monomer unit, the polymer, and / or the polymer dots. In some embodiments, the absorbent monomer units, the polymer, and / or the polymer dots have an absorption band that is a range of wavelengths, frequencies, or energies from the spectrum of the absorbed electromagnetic radiation (i.e., the "absorption spectrum").
[0240] In some embodiments, the energy absorbed by the absorptive monomer unit is transferred to the emissive monomer unit. The polymer may include an absorptive monomer unit, an emissive monomer unit, and an energy transfer monomer unit. For example, the energy absorbed by the absorptive monomer unit can be transferred to the energy transfer monomer unit and then from the energy transfer monomer unit to the emissive monomer unit. The energy can be transferred from the absorptive monomer unit to the emissive monomer unit, or first to the energy transfer monomer unit and then to the emissive monomer unit, by intermolecular or intramolecular energy transfer. Non-limiting examples of intermolecular and intramolecular energy transfer include, for example, through-chain energy transfer, through-bond energy transfer, Förster resonance energy transfer (FRET), Dexter energy transfer, cascade energy transfer, and fluorescence energy transfer. The transferred energy can excite the emissive monomer unit from its ground state (initial state) to an excited state. An "emissive monomer unit" is a unit that emits electromagnetic radiation, the emission of which causes the monomer unit to return from the excited state to the ground state. In some embodiments, the emissive monomer unit, the polymer, and / or the polymer dots have an emission band, which is a range of wavelengths, frequencies, or energies from the spectrum of the emitted electromagnetic radiation (i.e., the "emission spectrum"). In some embodiments, the emission spectrum can vary from the ultraviolet to the infrared region. As used herein, an "energy transfer monomer unit" is a monomer unit different from the absorptive monomer unit and the emissive monomer unit (e.g., a third or additional monomer unit in the polymer that transfers energy and is different from the absorptive monomer unit and the emissive monomer unit), which can transfer energy to the emissive monomer unit through an intra-chain or inter-chain mechanism. For example, the energy transfer can occur through FRET (Förster resonance energy transfer), inter-chain energy transfer, through-bond energy transfer.
[0241] In some embodiments, the absorptive unit includes an absorptive monomer unit. In certain embodiments, the absorptive unit includes a narrow-band absorptive monomer unit. An absorptive unit including a narrow-band absorptive monomer unit may be referred to as a narrow-band absorptive unit.
[0242] The polymers of the present disclosure have a narrow absorption spectrum. In some embodiments, the width of the absorption spectrum (also referred to herein as the "absorption width") can be characterized by its full width at a percentage of its maximum value (e.g., the full width at 15% of the absorbance maximum, or the full width at 10% of the absorbance maximum). The absorbance maximum of the absorption spectrum is defined as the maximum height reached by the absorbance intensity on the baseline of the absorption peak. In certain embodiments, the true baseline is used, and the maximum absorbance is calculated as the intensity difference between the main peak of the absorbance curve and the baseline ( Fig. 9A ). The maximum absorbance can be expressed as A max. In some embodiments, the absorbance curve is a perfect Gaussian curve. In other embodiments, the absorbance curve is not a perfect Gaussian curve and may have a starting intensity value different from the ending intensity value (i.e., the intensity at the start of the absorbance curve may be higher than the intensity at the end of the absorbance curve)( Fig. 9B ). In some embodiments, a corrected baseline is used and the maximum absorbance is calculated as the intensity difference between the peak of the absorbance curve and the corrected baseline( Fig. 9B ). The corrected baseline can be set to the lowest value of the absorbance curve intensity, as Fig. 9B shown. In certain embodiments, the corrected baseline value can be set to the lowest value of the absorbance curve intensity in the range of 350 nm to 1000 nm. The maximum absorption peak can be in the wavelength range from ultraviolet to infrared. In some embodiments, the maximum absorption peak is in the range of 380 nm to 1200 nm. In certain embodiments, the maximum absorption peak is in the range of 380 nm to 1200 nm, 400 nm to 1100 nm, 500 nm to 1000 nm, 600 nm to 900 nm, 380 nm to 1100 nm, 380 nm to 1000 nm, 380 nm to 950 nm, 380 nm to 900 nm, 380 nm to 850 nm, 380 nm to 800 nm, 380 nm to 750 nm, 380 nm to 700 nm, or 400 nm to 700 nm.
[0243] As a non-limiting example, a sample with a perfect Gaussian curve may have a maximum absorbance of 1.00 AU and a baseline value that is always 0 AU. The full width at 15% of the maximum absorbance will be the width of the curve at 0.15 AU (i.e., 15% of the maximum value). Similarly, the full width at 10% of the maximum absorbance will be the width at 0.10 AU. The full width at 17% of the maximum absorbance will be the width at 0.17 AU. Thus, the full width at various percentages of the absorbance maximum can be calculated. All of the above-defined parameters, such as the absorption spectrum and the full width at the maximum absorbance percentage, can be experimentally measured. In the present disclosure, these parameters can be specifically used to characterize narrowband absorptive Pdots.
[0244] In certain embodiments, the absorption spectrum has a distinguishable absorbance maximum curve. The distinguishable absorbance maximum curve may not overlap with other absorbance curves, thereby improving target excitation and multiplex applications. In some embodiments, the distinguishable absorbance curve may be characterized by having no significant spectral overlap with other absorbance curves (i.e., the absorption peak has an integrated area of less than 1% overlapping with an adjacent absorption peak). In certain embodiments, the distinguishable absorbance curve may have a small spectral overlap. In some embodiments, the overlapping area of the distinguishable absorbance maximum curve is less than 5% of the integrated area of any adjacent peak, less than 10% of the integrated area of any adjacent peak, less than 15% of the integrated area of any adjacent peak, less than 20% of the integrated area of any adjacent peak, less than 25% of the integrated area of any adjacent peak, less than 30% of the integrated area of any adjacent peak, less than 35% of the integrated area of any adjacent peak, or less than 40% of the integrated area of any adjacent peak. In some embodiments, the distinguishable absorbance curve may be baseline-separated. In certain embodiments, the distinguishable absorbance curve may be 100% baseline-separated, greater than 99% baseline-separated, greater than 98% baseline-separated, greater than 97% baseline-separated, greater than 96% baseline-separated, greater than 95% baseline-separated, greater than 90% baseline-separated, greater than 85% baseline-separated, greater than 80% baseline-separated, greater than 75% baseline-separated, greater than 70% baseline-separated, greater than 65% baseline-separated, or greater than 60% baseline-separated. In certain embodiments, the distinguishable absorbance curve is baseline-separated (i.e., the spectrum returns to the baseline between the peaks).
[0245] In some embodiments, the absorption spectrum includes multiple distinguishable curves. For example, the absorption spectrum may have 2 distinguishable curves, 3 distinguishable curves, or more than 3 distinguishable curves. In some embodiments, the maximum absorbance is calculated as the intensity difference between the peak of the maximum absorbance curve and the baseline ( Fig. 9C)。The maximum absorbance curve and other distinguishable curves can be in the wavelength range from ultraviolet to infrared. In some embodiments, the maximum absorbance curve and other distinguishable curves are in the range of 380 nm to 1200 nm. In certain embodiments, the maximum absorbance curve and other distinguishable curves are in the range of 380 nm to 1200 nm, 400 nm to 1100 nm, 500 nm to 1000 nm, 600 nm to 900 nm, 380 nm to 1100 nm, 380 nm to 1000 nm, 380 nm to 950 nm, 380 nm to 900 nm, 380 nm to 850 nm, 380 nm to 800 nm, 380 nm to 750 nm, 380 nm to 700 nm, or 400 nm to 700 nm. In some embodiments, the maximum absorbance curve can have a starting intensity value different from the ending intensity value (i.e., the intensity at the start of the absorbance curve can be higher than the intensity at the end of the absorbance curve)( Fig.9D )。In some embodiments, a corrected baseline is used, and the maximum absorbance is calculated as the intensity difference between the peak of the absorbance curve and the corrected baseline( Fig.9D )。
[0246] The corrected baseline can be set to the lowest value of the absorbance curve intensity. In certain embodiments, the corrected baseline is set to the lowest value of the absorbance curve intensity that is flat (i.e., has a slope of approximately 0). Generally, the lowest value of the absorbance curve intensity is in the red wavelength portion of the spectrum relative to the absorbance curve (i.e., to the right of the peak of the absorbance curve, having a wavelength value higher than the peak of the absorbance curve). In specific embodiments, the corrected baseline value can be set to the lowest value of the absorbance curve intensity in the range of 350 nm to 1000 nm.
[0247] In certain embodiments, the absorption peaks of multiple distinguishable absorbance curves on the spectrum are separated by wavelength values. In some embodiments, the peaks of multiple distinguishable absorbance curves on the spectrum are separated by more than 20 nm, more than 30 nm, more than 40 nm, more than 50 nm, more than 60 nm, more than 70 nm, more than 80 nm, more than 90 nm, more than 100 nm, more than 110 nm, more than 120 nm, more than 130 nm, more than 140 nm, more than 150 nm, more than 200 nm, more than 250 nm, more than 300 nm, more than 350 nm, more than 400 nm, more than 450 nm, or more than 500 nm.
[0248] In some embodiments, the characteristics of multiple distinguishable curves may lie in having no significant spectral overlap with other distinguishable absorbance curves (i.e., each distinguishable absorption peak has an integrated area overlapping with an adjacent absorption peak of less than 1%). In certain embodiments, each distinguishable absorbance curve may have a small spectral overlap. In some embodiments, for each distinguishable absorbance maximum curve among the multiple distinguishable curves, the overlapping area is less than 5% of the integrated area of any adjacent peak, less than 10% of the integrated area of any adjacent peak, less than 15% of the integrated area of any adjacent peak, less than 20% of the integrated area of any adjacent peak, less than 25% of the integrated area of any adjacent peak, less than 30% of the integrated area of any adjacent peak, less than 35% of the integrated area of any adjacent peak, or less than 40% of the integrated area of any adjacent peak. In some embodiments, each distinguishable absorbance curve may be baseline-separated. In certain embodiments, each distinguishable absorbance curve may be 100% baseline-separated, greater than 99% baseline-separated, greater than 98% baseline-separated, greater than 97% baseline-separated, greater than 96% baseline-separated, greater than 95% baseline-separated, greater than 90% baseline-separated, greater than 85% baseline-separated, greater than 80% baseline-separated, greater than 75% baseline-separated, greater than 70% baseline-separated, greater than 65% baseline-separated, or greater than 60% baseline-separated. In certain embodiments, each distinguishable absorbance curve is baseline-separated (i.e., the spectrum returns to the baseline between the peaks).
[0249] The absorption wavelength of the polymer dots can vary from the ultraviolet to the infrared region. In a preferred embodiment, the polymer dots include absorbent monomer units and emissive monomer units. As provided herein, the chemical composition and structure of the polymer dots can be adjusted to obtain a small bandwidth of nanoparticle absorption. Other species such as narrow-band absorption units, narrow-band absorbent monomer units, metal complexes, inorganic materials, or emissive units can be blended or chemically crosslinked within the polymer dots to obtain a small bandwidth of nanoparticle absorption.
[0250] Narrow band absorbing polymer dots comprising at least one polymer
[0251] In certain embodiments, the present disclosure provides nanoparticles comprising a polymer, wherein the polymer comprises both absorptive monomer units and emissive monomer units, and the nanoparticles have an absorption width less than 150 nm at 10% (or in some embodiments, at 15%) of the absorbance maximum. In some embodiments, the absorptive monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof. In some embodiments, the absorptive monomer units include BODIPY, BODIPY derivatives, or any combination thereof.
[0252] In some embodiments, the present disclosure provides nanoparticles comprising a polymer, wherein the polymer comprises both absorptive monomer units and emissive monomer units, the absorptive monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof (e.g., the absorptive monomer units include BODIPY, BODIPY derivatives, or any combination thereof). In some embodiments, the absorptive monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In certain embodiments, the nanoparticles have an absorption width less than 150 nm at 10% (or in some embodiments, at 15%) of the absorbance maximum.
[0253] In some embodiments, the nanoparticle further comprises a polymer, the polymer comprising one or more monomer units different from the absorbent monomer units and the emissive monomer units. When the polymer further comprises one or more monomer units different from the absorbent monomer units and the emissive monomer units, the nanoparticle has an absorption width at 10% of the absorbance maximum of less than 150 nm. The one or more monomer units different from the absorbent monomer units and the emissive monomer units may include general monomer units; functional monomer units; energy transfer monomer units; additional second absorbent monomer units (different from the above absorbent monomer units); or any combination thereof. The general monomer units may be, for example, functional monomer units and / or energy transfer monomer units. The functional monomer units provide specific functions, such as providing hydrophilicity, hydrophobicity, amphiphilicity, fluorophilicity, reactive functional groups or any combination thereof to the monomer units. For example, the functional monomer units may include reactive functional groups that can be used for, for example, conjugating biomolecules. In some embodiments, the functional monomer units may provide hydrophilicity to the polymer, provide hydrophobicity to the polymer and / or improve the biocompatibility of the polymer. For example, the functional monomer units may be hydrophilic monomer units. In some embodiments, the functional monomer units may be hydrophilic monomer units that do not have reactive functional groups suitable for bioconjugation (e.g., conjugation under conditions that do not adversely affect the structure or function of biomolecules).
[0254] In some embodiments, the narrowband absorbent polymer comprises a first absorbent monomer unit, an emissive monomer unit, and an energy transfer unit. In certain embodiments, the narrowband absorbent polymer comprises a first absorbent monomer unit, an emissive monomer unit, an energy transfer unit, and a functional monomer unit. In some embodiments, the narrowband absorbent polymer comprises a first absorbent monomer unit, an emissive monomer unit, and a functional monomer unit. In certain embodiments, the narrowband absorbent polymer comprises a first absorbent monomer unit, a second absorbent monomer unit, and an emissive monomer unit. In some embodiments, the narrowband absorbent polymer comprises two monomer units different from the absorbent monomer units and the emissive monomer units.
[0255] A polymer comprising absorbent monomer units and emissive monomer units may be referred to as an "absorbent and emissive polymer".
[0256] In certain embodiments, the polymer has a backbone that includes absorbent monomer units, has side chains that include absorbent monomer units, has termini that include absorbent monomer units, or any combination thereof. In certain embodiments, the polymer has a backbone that includes emissive monomer units, has side chains that include emissive monomer units, has termini that include emissive monomer units, or any combination thereof. In certain embodiments, the polymer has a backbone that includes absorbent units, has side chains that include absorbent units, has termini that include absorbent units, or any combination thereof. In certain embodiments, the polymer has a backbone that includes emissive units, has side chains that include emissive units, has termini that include emissive units, or any combination thereof. In some embodiments, the absorbent units can include one or more monomer units that together act as an absorbent moiety. In some embodiments, the emissive units can include one or more monomer units that together act as an emissive moiety.
[0257] These polymers can be linear, branched, hyperbranched, dendrimeric, crosslinked, random, block, grafted, or of any structural type. In certain embodiments, the polymer is a copolymer and can be a block copolymer, random copolymer, periodic copolymer, statistical copolymer, gradient copolymer, alternating copolymer, or any combination thereof.
[0258] In certain embodiments, the polymer is a semiconductor polymer. In certain embodiments, the polymer backbone is semiconducting.
[0259] In some embodiments, the narrowband absorbent polymer does not include a β-phase structure. In certain embodiments, the narrowband absorbent polymer does not include fluorene or fluorene-based monomer units. In some embodiments, the Pdot nanoparticles do not include any polymer having a β-phase structure. In certain embodiments, the Pdot nanoparticles do not include any polymer having fluorene or fluorene-based monomer units.
[0260] Narrow band absorbing polymer dots comprising at least two polymers
[0261] In certain embodiments, the present disclosure provides nanoparticles that include a first polymer having absorbent monomer units and a second polymer having emissive monomer units. The absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum can be less than 150 nm. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In some embodiments, the first polymer and the second polymer are the same polymer.
[0262] In certain embodiments, the present disclosure provides nanoparticles that include a first polymer and a second polymer, the first polymer including absorbent monomer units that include BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaraines, squaraine derivatives, or any combination thereof, and the second polymer including emissive monomer units. In some embodiments, the absorbent monomer units include BODIPY, BODIPY derivatives, or any combination thereof. In certain embodiments, the absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum is less than 150 nm. In some embodiments, the first polymer and the second polymer are the same polymer.
[0263] A polymer that includes absorbent monomer units can be referred to as an "absorbent polymer", and a polymer that includes emissive monomer units can be referred to as an "emissive polymer".
[0264] In some embodiments, the first polymer has a backbone that includes absorbent monomer units, a side chain that includes absorbent monomer units, an end (i.e., terminal end) that includes absorbent monomer units, or any combination thereof. The absorbent monomer units can be crosslinked to the polymer backbone. The absorbent units can include absorbent monomer units and can be crosslinked and / or covalently linked to the polymer backbone.
[0265] These polymers can be linear, branched, hyperbranched, dendritic, crosslinked, random, block, grafted, or of any structural type. In certain embodiments, the polymer is a copolymer and can be a block copolymer, random copolymer, periodic copolymer, statistical copolymer, gradient copolymer, alternating copolymer, or any combination thereof.
[0266] In some embodiments, the first polymer is a semiconductor polymer. In certain embodiments, the second polymer is a semiconductor polymer. In some embodiments, each of the first polymer and the second polymer is a semiconductor polymer. In particular embodiments, the polymer backbone is semiconducting.
[0267] In some embodiments, the narrowband absorptive nanoparticles have a mass ratio of a first polymer comprising absorptive monomer units to a second polymer comprising emissive monomer units. In certain embodiments, the mass ratio of the first polymer to the second polymer is greater than 1:1, greater than 2:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1, greater than 8:1, greater than 9:1, greater than 10:1, greater than 20:1, greater than 30:1, greater than 40:1, greater than 50:1, or greater than 100:1. In certain embodiments, the mass ratio of the first polymer to the second polymer is 1:1 or greater, 2:1 or greater, 3:1 or greater, 4:1 or greater, 5:1 or greater, 6:1 or greater, 7:1 or greater, 8:1 or greater, 9:1 or greater, 10:1 or greater, 20:1 or greater, 30:1 or greater, 40:1 or greater, 50:1 or greater, or 100:1 or greater. As a non-limiting example, nanoparticles comprising 1 μg of absorptive (first) polymer and 0.5 μg of emissive (second) polymer will have a mass ratio of the first polymer to the second polymer of 2:1.
[0268] Composition of polymer
[0269] In certain embodiments, the nanoparticles comprise a first polymer and a second polymer, wherein the first polymer comprises absorptive monomer units and the second polymer comprises emissive monomer units. The first polymer may be referred to as an "absorptive polymer", an "absorbing polymer", or a "light-absorbing polymer", and the second polymer may be referred to as an "emissive polymer", an "emitting polymer", or a "light-emitting polymer". In certain embodiments, the first polymer is a narrowband absorptive polymer.
[0270] In some embodiments, the narrowband absorptive polymer does not include a β-phase structure. In certain embodiments, the narrowband absorptive polymer does not include fluorene or fluorene-based monomer units. In some embodiments, the Pdot nanoparticles do not include any polymer having a β-phase structure. In certain embodiments, the Pdot nanoparticles do not include any polymer having fluorene or fluorene-based monomer units.
[0271] In certain embodiments, the nanoparticles comprise an absorptive polymer and an emissive polymer, wherein the polymers are physically blended and / or chemically crosslinked. In some embodiments, the nanoparticles have intrachain and interchain energy transfer. In certain embodiments, the combination of intrachain and interchain energy transfer can increase the quantum yield of the polymer dots. In certain embodiments, the nanoparticles exhibit narrowband absorption. In various embodiments, the polymer nanoparticles comprise blends of polymers that provide structural and / or energy transfer support. For example, Pdots comprising semiconductor polymers or polymers comprising emissive monomer units and absorptive monomer units linked by a semiconductor backbone can have enhanced energy transfer, e.g., by fluorescence resonance energy transfer, through-bond energy transfer, and / or through-chain energy transfer.
[0272] Absorbent polymers
[0273] In some embodiments, the absorptive polymer is a homopolymer comprising only absorptive monomer units (e.g., Figure 1A ). In some embodiments, the absorptive polymer is a two-unit copolymer comprising one absorptive monomer unit and one general monomer unit (e.g., G, G1, G2, and / or G2') ( Figure 1B ). The general monomer unit can comprise a functional monomer unit and / or an energy transfer monomer unit. In some embodiments, the general monomer unit can be broadband emissive (e.g., in the wavelength range of about 400 nm to about 1000 nm). In some embodiments, the general monomer unit can be broadband absorptive (e.g., in the wavelength range of about 350 nm to about 800 nm). In some embodiments, the general monomer unit can be semiconductor. The general monomer unit can be an energy acceptor, and the absorptive monomer unit can be an energy donor. Energy transfer within the Pdot can result in luminescent emission. In some embodiments, energy transfer within the Pdot can result in fluorescent emission. In some embodiments, the absorptive polymer is a three-unit copolymer that comprises one absorptive monomer unit and two general monomer units such as general monomer unit 1 and general monomer unit 2 (e.g., selected from G, G1, G2, and / or G2') ( Figure 1C)。The absorbent monomer unit can be an energy donor, the general monomer unit 1 can be an energy acceptor and / or an energy donor, and the general monomer unit 2 can also be an energy acceptor of the absorbent monomer unit and / or an energy donor of the emitter. In some embodiments, the general monomer unit 2 can be an energy donor of the general monomer unit 1 or the emitter, and at the same time can be an energy acceptor of the absorbent monomer unit. Both the general monomer unit 1 and the general monomer unit 2 can be semiconductor. Both the general monomer unit 1 and the general monomer unit 2 can be emissive. However, multi-step energy transfer within the Pdot can result in emission with a high quantum yield. In certain embodiments, the absorbent polymer can be a heteropolymer, such as a multi-unit (≥3) copolymer, which includes at least one type of absorbent monomer unit such that the final Pdot provides narrow-band absorption.
[0274] In some embodiments, the absorbent polymer is a copolymer that includes absorbent units crosslinked to the side chains ( Figure 1D )。The copolymer can include 2 types of general monomer units, 3 types of general monomer units, 4 types of general monomer units, 5 types of general monomer units, or more than 5 types of general monomer units (e.g., selected from G, G1, G2, and / or G2'). However, the absorbent polymer can include at least one type of absorbent unit in the side chain. The copolymer backbone can be an energy acceptor, and the absorbent unit can be an energy donor. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the absorbent polymer is a homopolymer that includes absorbent units crosslinked to the side chains ( Figure 1E )。The homopolymer backbone can be an energy acceptor, and the absorbent unit can be an energy donor. Energy transfer within the Pdot can result in luminescent emission. In some embodiments, the luminescent emission can have narrow-band emission. In certain embodiments, the narrow-band absorbent nanoparticles include narrow-band emissive monomer units, narrow-band emissive polymers, or any combination thereof. Examples of narrow-band emissive monomer units, narrow-band emissive polymers, and general monomer units are provided herein and can be found in International Application PCT / US2012 / 071767, which is incorporated herein by reference.
[0275] In some embodiments, the absorbent polymer can be attached to at least one end of the polymer, or in the case of a linear polymer, to both ends ( Figure 1F), or, in the case of a branched polymer, a polymer of absorbent monomer units attached to all termini. The polymer can include, for example, one type of general monomer unit (e.g., any of G, G1, G2, or G2'), or two types of general monomer units (e.g., any of G, G1, G2, or G2'), or three types of general monomer units, or more than three types of general monomer units. The polymer backbone can be an energy acceptor, and the absorbent unit can be an energy donor. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the absorbent polymer can be a homopolymer or a heteropolymer that includes absorbent units attached to the polymer termini. The homopolymer or heteropolymer backbone can be an energy acceptor, and the absorbent unit can be an energy donor. Energy transfer within the Pdot can result in luminescent emission.
[0276] Figure 1G to Figure 1L Other examples of the schematic structure of the absorbent polymer are shown, which can include, for example, general monomer units (G) as the acceptor and donor and absorbent monomer units (A) as the donor. In some aspects, the donor can absorb energy and transfer the energy directly or indirectly (e.g., through cascade energy transfer) to the emissive monomer unit or emissive polymer. In addition to the general monomer units and absorbent monomer units, these polymers can also include functional monomer units, functional groups, and / or functional units (F), which provide reactive functional groups for, for example, chemical reactions and bioconjugation reactions, or provide other functions unrelated to chemical reactions, such as imparting hydrophilicity or amphiphilicity to some monomer units. The functional monomer units, functional groups, and / or functional units can include, for example, halocarbonyl, hydroxyl, aldehyde, alkenyl, alkynyl, anhydride, formamide, amine, azo compound, carbonate, carboxylate, carboxyl, cyanate, ester, haloalkane, imine, isocyanate, nitrile, nitro, phosphino, phosphate, phosphonate, pyridyl, sulfonyl, sulfonic acid, sulfoxide, thiol group, or any combination thereof, and reactive groups that can undergo click chemical reactions, such as alkynes, strained alkynes, azides, dienes, alkenes, cyclooctynes, phosphine groups, or any combination thereof. The functional monomer units can be copolymerized with the general monomer units and absorbent monomer units (e.g., Figure 1G ), or crosslinked with these two monomer units. The functional monomer units can be used as one terminus (or both termini) of the polymer (e.g., Figure 1H and Figure 1K ). The functional groups can be included in the general monomer units or absorbent monomer units (e.g., Fig. 1I ). In some embodiments, the absorbent monomer units can also be copolymerized with any of the general polymers to synthesize absorbent copolymers or heteropolymers containing more than two types of monomer units (e.g., Figure 1J ). The absorbent monomer units can be covalently attached to the side chains of the polymer (e.g., Figure 1L )。In some embodiments, the absorbent unit may be covalently attached to the end of the polymer. In some embodiments, the absorbent unit may be physically mixed or blended with a conventional semiconductor polymer to form narrow-band absorbent polymer dots. In one embodiment, the absorbent unit may be covalently crosslinked with a conventional semiconductor polymer to form narrow-band absorbent polymer dots. The conventional semiconductor polymer may absorb energy and transfer the energy directly or indirectly (e.g., through cascaded energy transfer) to the emissive monomer unit or emissive polymer.
[0277] All of the absorbent polymers described above in Figures 1A to 1L may be physically blended or chemically crosslinked, for example, with one or more common broadband absorbent and / or emissive polymers. In some aspects, the polymers may be energy donors and acceptors, and the absorbent polymers may be energy donors. Multiple-step energy transfer may occur from the absorbent polymer to the luminescent polymer, such that the polymer dots provide luminescent emission. Chemical crosslinking between the polymers may use functional reactive groups such as halocarbonyl, hydroxyl, aldehyde, alkenyl, alkynyl, anhydride, formamide, amine, azo compound, carbonate, carboxylate, carboxyl, cyanate, ester, haloalkane, imine, isocyanate, nitrile, nitro, phosphino, phosphate, phosphonate, pyridyl, sulfonyl, sulfonic acid, sulfoxide, thiol group, or any combination thereof, as well as reactive groups that can undergo click chemical reactions such as alkyne, strained alkyne, azide, diene, alkene, cyclooctyne, phosphine group, or any combination thereof. These functional groups may be attached to the side chains and / or ends of each polymer chain.
[0278] Emissive polymers
[0279] In some embodiments, the emissive polymer is a homopolymer that includes only emissive monomer units (e.g., Figure 2A )。In some embodiments, the emissive polymer is a two-unit copolymer that includes one emissive monomer unit and one common monomer unit (e.g., G, G1, G2, and / or G2') Figure 2B)。The general monomer unit can include a functional monomer unit and / or an energy transfer monomer unit. In some embodiments, the general monomer unit can be broadband absorbent. In some embodiments, the general monomer unit can be broadband emissive. In some embodiments, the general monomer unit can be semiconducting. The general monomer unit can be an energy donor, and the emissive monomer unit can be an energy acceptor. Energy transfer within the Pdot can result in luminescent emission. In some embodiments, energy transfer within the Pdot can result in fluorescent emission. In some embodiments, the emissive polymer is a terpolymer that includes one emissive monomer unit and two general monomer units such as general monomer unit 1 and general monomer unit 2 (e.g., selected from G, G1, G2, and / or G2')( Figure 2C )。The emissive monomer unit can be an energy acceptor, general monomer unit 1 can be an energy donor, and general monomer unit 2 can also be a donor for the emissive monomer unit. In some embodiments, general monomer unit 2 can be an energy acceptor for general monomer unit 1 and can simultaneously be an energy donor for the emissive monomer unit. Both general monomer unit 1 and general monomer unit 2 can be semiconducting. Both general monomer unit 1 and general monomer unit 2 can be emissive. Multistep energy transfer within the Pdot can result in narrowband emission. In certain embodiments, the emissive polymer can be a heteropolymer, such as a multi-unit (≥3) copolymer, that includes at least one type of emissive monomer unit such that the final Pdot provides luminescent emission.
[0280] In some embodiments, the emissive polymer is a copolymer that includes emissive units crosslinked to the side chains( Figure 2D )。The copolymer can include 2 types of general monomer units, 3 types of general monomer units, 4 types of general monomer units, 5 types of general monomer units, or more than 5 types of general monomer units (e.g., selected from G, G1, G2, and / or G2'). However, the emissive polymer can include at least one type of emissive unit in the side chain. The copolymer backbone can be an energy donor, and the emissive unit can be an energy acceptor. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the emissive polymer is a homopolymer that includes emissive units crosslinked to the side chains( Figure 2E )。The homopolymer backbone can be an energy donor, and the emissive unit can be an energy acceptor. Energy transfer within the Pdot can result in luminescent emission. In some embodiments, the luminescent emission is narrowband emission.
[0281] In some embodiments, the emissive polymer can be one that includes attachment to at least one end of the polymer, or in the case of a linear polymer, attachment to both ends( Figure 2F), or, in the case of a branched polymer, a polymer of emissive monomer units attached to all termini. The polymer can include, for example, one type of general monomer unit (e.g., any of G, G1, G2, or G2'), or two types of general monomer units (e.g., any of G, G1, G2, or G2'), or three types of general monomer units, or more than three types of general monomer units. The polymer backbone can be an energy donor and the emissive unit can be an energy acceptor. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the emissive polymer can be a homopolymer or a heteropolymer that includes emissive units attached to the polymer termini. The homopolymer or heteropolymer backbone can be an energy donor and the emissive unit can be an energy acceptor. Energy transfer within the Pdot can result in luminescent emission.
[0282] Figure 2G to Figure 2L Other examples of the schematic structures of emissive polymers are shown, which can include, for example, general monomer units (G) as acceptors and donors and emissive monomer units (E) as acceptors. In some aspects, the general monomer units can absorb energy and transfer the energy directly or indirectly (e.g., through cascaded energy transfer) to the emissive monomer units or emissive polymers. In addition to the general monomer units and emissive monomer units, these polymers can also include functional monomer units, functional groups, and / or functional units (F), which provide reactive functional groups for, for example, chemical reactions and bioconjugation reactions. The functional monomer units, functional groups, and / or functional units can include, for example, halocarbonyl, hydroxyl, aldehyde, alkenyl, alkynyl, anhydride, formamide, amine, azo compound, carbonate, carboxylate, carboxyl, cyanate, ester, haloalkane, imine, isocyanate, nitrile, nitro, phosphino, phosphate, phosphonate, pyridyl, sulfonyl, sulfonic acid, sulfoxide, thiol group, or any combination thereof, and reactive groups that can undergo click chemical reactions, such as alkynes, strained alkynes, azides, dienes, alkenes, cyclooctynes, phosphine groups, or any combination thereof. The functional monomer units can be copolymerized with the general monomer units and absorptive monomer units (e.g., Figure 2G ), or crosslinked with these two monomer units. The functional monomer units can be used as one terminus (or both termini) of the polymer (e.g., Figure 2H and Figure 2K ). The functional monomer units can provide specific functions, such as providing hydrophilicity, hydrophobicity, amphiphilicity, fluorophilicity, reactive functional groups, or any combination thereof to the monomer units. The functional groups can be included in the general monomer units or emissive monomer units (e.g., Fig.2I ). In some embodiments, the emissive monomer units can also be copolymerized with any of the general polymers to synthesize emissive copolymers or heteropolymers containing more than two types of monomer units (e.g., Figure 2J)。The emissive monomer units can be covalently linked to the side chains of the polymer (e.g., Figure 2L ). In some embodiments, the emissive units can be covalently linked to the termini of the polymer. In some embodiments, the emissive units can be physically blended or co - blended with a conventional semiconductor polymer to form narrow - band absorptive polymer dots with luminescent emission. In one embodiment, the emissive units can be covalently cross - linked with a conventional semiconductor polymer to form luminescent polymer dots. The conventional semiconductor polymer can absorb energy and transfer the energy directly or indirectly (e.g., through cascade energy transfer) to the emissive monomer units or emissive polymers.
[0283] All of the emissive polymers described above in Figures 2A to 2L can be physically co - blended or chemically cross - linked, for example, with one or more common emissive and / or absorptive polymers. In some aspects, the polymer can be an energy donor and acceptor, and the emissive polymer can be an energy acceptor. Multistep energy transfer can occur from the absorptive polymer to the luminescent polymer such that the polymer dots provide luminescent emission. Chemical cross - linking between polymers can use functional reactive groups such as halocarbonyl, hydroxyl, aldehyde, alkenyl, alkynyl, anhydride, formamide, amine, azo compound, carbonate, carboxylate, carboxyl, cyanate, ester, haloalkane, imine, isocyanate, nitrile, nitro, phosphino, phosphate, phosphonate, pyridyl, sulfonyl, sulfonic acid, sulfoxide, thiol group or any combination thereof, and reactive groups that can undergo click chemical reactions such as alkyne, strained alkyne, azide, diene, alkene, cyclooctyne, phosphine group or any combination thereof. These functional groups can be attached to the side chains and / or termini of each polymer chain.
[0284] Absorbing and emissive polymers
[0285] In certain embodiments, the nanoparticles comprise a polymer having both absorptive monomer units and emissive monomer units. In some embodiments, a polymer that simultaneously comprises absorptive monomer units and emissive monomer units is referred to as an "absorptive and emissive polymer" or an "emissive and absorptive polymer". In certain embodiments, the absorptive and emissive polymer is a narrow - band absorptive polymer.
[0286] In some embodiments, the polymer is a two - unit random copolymer and comprises absorptive monomer units and emissive monomer units ( Figure 3A ). In certain embodiments, the polymer is a two - unit alternating copolymer comprising absorptive monomer units and emissive monomer units ( Figure 3B ). In some embodiments, the absorptive monomer units act as energy donors and the emissive monomer units act as energy acceptors. Energy can be transferred from the absorptive monomer units to the emissive monomer units, resulting in the emission of luminescence.
[0287] In some embodiments, the polymer comprises absorptive monomer units and emissive monomer units, and further comprises at least one general monomer unit (e.g., G, G1, G2, and / or G2')( FIG. 3C to FIG. 3N ). The general monomer unit may comprise functional monomer units and / or energy transfer monomer units. In certain embodiments, the polymer is a three-unit alternating copolymer comprising emissive monomer units, general monomer units, and absorptive monomer units( Figure 3C ). In other embodiments, the polymer is a two-unit alternating copolymer comprising absorptive monomer units and general monomer units, and the emissive monomer units are located at the termini( Figure 3D ). In some embodiments, the polymer is a two-unit alternating copolymer comprising emissive monomer units and general monomer units, and the absorptive monomer units are located at the termini( Figure 3E ). In some embodiments, the polymer comprises repeating general monomer units, wherein both the emissive monomer units and the absorptive monomer units are located at the termini( Figure 3F ). In other embodiments, the polymer is a three-unit random copolymer comprising emissive monomer units, general monomer units, and absorptive monomer units( Figure 3G ). In some embodiments, the general monomer unit can be broadband absorptive. In some embodiments, the general monomer unit can be broadband emissive. In some embodiments, the general monomer unit can be semiconducting. The general monomer unit can be an energy donor and an energy acceptor, the absorptive monomer unit can be an energy donor, and the emissive monomer unit can be an energy acceptor. Energy transfer within the Pdot can result in luminescent emission. In some embodiments, energy transfer within the Pdot can result in fluorescent emission. Multistep energy transfer within the Pdot can result in narrowband emission. As a non-limiting example, energy absorbed by the absorptive monomer unit (acting as an energy donor) can be transferred to the general monomer unit (acting as an energy acceptor), and then further transferred from the general monomer unit (acting as an energy donor) to the emissive monomer unit (acting as an energy acceptor). In some embodiments, the general monomer unit may comprise functional monomer units to provide specific functions, such as providing hydrophilicity, hydrophobicity, amphiphilicity, fluorophilicity, reactive functional groups, or any combination thereof to the monomer units. In certain embodiments, the emissive polymer can be a heteropolymer, such as a multi-unit (≥3) copolymer, the heteropolymer comprising at least one type of emissive monomer unit such that the final Pdot provides luminescent emission.
[0288] In certain embodiments, the polymer comprises absorptive monomer units, emissive monomer units, and at least two general monomer units (e.g., G, G1, G2, and / or G2')( Figures 3H to 3N)。The general monomer units can include functional monomer units and / or energy transfer monomer units. In some embodiments, the polymer is a four-unit alternating copolymer comprising emissive monomer units, a first general monomer unit, a second general monomer unit, and absorptive monomer units( Figure 3H )。In certain embodiments, the general monomer units act as energy donors and acceptors and can transfer energy along the polymer backbone. In other embodiments, the polymer is a four-unit random copolymer comprising emissive monomer units, a first general monomer unit, a second general monomer unit, and absorptive monomer units( Fig. 3I )。The absorptive monomer units can be energy donors, the emissive monomer units can be energy acceptors, the general monomer unit 1 can be an energy donor and acceptor, and the general monomer unit 2 can also be an energy donor and acceptor. In some embodiments, the general monomer unit 1 can be an energy acceptor of the absorptive monomer unit and at the same time an energy donor of the general monomer unit 2, while the general monomer unit 2 can be an energy acceptor of the general monomer unit 1 and at the same time an energy donor of the emissive monomer unit. Both the general monomer unit 1 and the general monomer unit 2 can be semiconducting. Both the general monomer unit 1 and the general monomer unit 2 can be emissive. Multi-step energy transfer within the Pdot can result in narrow-band emission. In certain embodiments, the absorptive and emissive polymers can be heteropolymers, such as multi-unit (≥3) copolymers, which include at least one type of emissive monomer unit such that the final Pdot provides luminescent emission.
[0289] In some embodiments, the absorptive polymer is a copolymer comprising absorptive units and / or emissive units crosslinked to the side chains( Figure 3J )。The copolymer can include 2 types of general monomer units, 3 types of general monomer units, 4 types of general monomer units, 5 types of general monomer units, or more than 5 types of general monomer units (e.g., selected from G, G1, G2, and / or G2'). The polymer can include at least one type of absorptive unit and / or emissive unit in the side chains. The copolymer backbone can be an energy acceptor, the absorptive units can be energy donors and energy acceptors, and the emissive monomer units can be energy acceptors. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the luminescent emission is narrow-band emission.
[0290] In some embodiments, the polymer is a copolymer comprising functional monomer units, functional groups, and / or functional units. In certain embodiments, the functional monomer units, functional groups, and / or functional units are attached to the general monomer units( Figure 3K)。Absorbing and emissive polymers can include, for example, general monomer units (G) as acceptors and donors, emissive monomer units (E) as acceptors, and absorbent monomer units (A) as donors. In some aspects, the general monomer units can absorb energy and transfer the energy directly or indirectly (e.g., through cascaded energy transfer) to the emissive monomer units. In addition to the general monomer units, absorbent monomer units, and emissive monomer units, these polymers can also include functional monomer units, functional groups, and / or functional units (F) that provide reactive functional groups for, e.g., chemical reactions and bioconjugation reactions, or provide other functions unrelated to chemical reactions, such as imparting hydrophilicity or amphiphilicity to some monomer units. Functional monomer units, functional groups, and / or functional units are as described above for Figures 2A to 2L stated. The functional monomer units can be copolymerized with the general monomer units and absorbent monomer units or crosslinking monomer units (e.g., Figure 3K ). The functional monomer units can be used as one (or both) of the termini of the polymer. The functional groups can be included in the general monomer units or emissive monomer units.
[0291] In some embodiments, the functional monomer units are monomer units with specific functions, such as providing hydrophilicity to the polymer, providing hydrophobicity to the polymer, providing amphiphilicity to the polymer, and / or improving the biocompatibility of the polymer. For example, the functional monomer units can be functionalized with hydrophilic, hydrophobic, amphiphilic groups, which can be reactive (e.g., suitable for bioconjugation) or non-reactive (e.g., not suitable for bioconjugation). The length, size, and nature of the hydrophilic, hydrophobic, and / or amphiphilic side chains can modify chain-chain interactions, control the packing of the polymer, and affect the colloidal stability and size of the polymer dots. The length, size, and nature of the hydrophilic, hydrophobic, and / or amphiphilic side chains can also affect the absorption, emission peak, emission bandwidth, fluorescence quantum yield, fluorescence lifetime, photostability, and other properties of the polymer and polymer dots. For example, many very hydrophilic functional groups can reduce the brightness of the polymer dots, and / or broaden the emission spectrum, and / or also adversely affect their colloidal stability and non-specific binding properties. In some embodiments, the functional monomer units include hydrophilic groups such as oligo(ethylene glycol), poly(ethylene glycol), poly(propylene glycol) (which is less hydrophilic than poly(ethylene glycol)), poly(ether), hydroxyl, and / or sulfate. In some embodiments, the functional monomer units include hydrophobic functional groups such as styrene, alkyl, and / or fatty acid chains.
[0292] In some embodiments, the emissive monomer units may also be copolymerized with any of the general polymers to synthesize an emissive copolymer or heteropolymer containing more than two types of monomer units. The emissive monomer units may be covalently linked to the side chains of the polymer. In some embodiments, the emissive units may be covalently linked to the termini of the polymer. In some embodiments, the emissive units may be physically mixed or blended with a conventional semiconductor polymer to form narrow-band absorptive polymer dots with luminescent emission. In one embodiment, the emissive units may be covalently crosslinked with a conventional semiconductor polymer to form luminescent polymer dots. The conventional semiconductor polymer may absorb energy and transfer the energy directly or indirectly (e.g., through cascaded energy transfer) to the emissive monomer units or emissive polymers.
[0293] In certain embodiments, the polymer is a copolymer comprising more than one absorptive unit. The copolymer may comprise absorptive monomer units linked to the polymer backbone and absorptive units linked to the polymer by crosslinking ( Figure 3L ). In some embodiments, the copolymer comprising both absorptive monomer units and absorptive units may further comprise functional monomer units, functional groups, and / or functional units linked to the polymer ( Figure 3M ). The polymer may comprise, for example, absorptive monomer units, functionalized first general monomer units, second general monomer units crosslinked with absorptive and / or emissive units, third general monomer units, and emissive monomer units ( Figure 3N ). The copolymer may comprise 3 types of general monomer units, 4 types of general monomer units, 5 types of general monomer units, 6 types of general monomer units, or more than 6 types of general monomer units (e.g., selected from G, G1, G2, G3, and / or G2'). The polymer may comprise at least one type of absorptive unit in the side chain. The copolymer backbone may be an energy acceptor, the absorptive units may be energy donors and energy acceptors, and the emissive monomer units may be energy acceptors. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the luminescent emission is narrow-band emission.
[0294] In certain embodiments, the polymer is a copolymer comprising more than one emissive unit. The copolymer may include emissive monomer units attached to the polymer backbone and emissive units attached to the polymer by crosslinking. In certain embodiments, the copolymer may include more than one emissive unit attached to the polymer by crosslinking. In some embodiments, a copolymer that includes both emissive monomer units and emissive units may further include functional monomer units, functional groups, and / or functional units attached to the polymer. The polymer may include, for example, emissive monomer units, functionalized first general monomer units, second general monomer units crosslinked with emissive and / or absorptive units, third general monomer units, and absorptive monomer units. The copolymer may include 3 types of general monomer units, 4 types of general monomer units, 5 types of general monomer units, 6 types of general monomer units, or more than 6 types of general monomer units (e.g., selected from G, G1, G2, G3, and / or G2'). The polymer may include at least one type of emissive unit in the side chain. The copolymer backbone may be an energy acceptor, the absorptive monomer unit may be an energy donor and an energy acceptor, the emissive unit may be an energy acceptor, and the emissive monomer unit may be an energy acceptor. Energy transfer within the Pdot results in luminescent emission. In some embodiments, the luminescent emission is narrowband emission.
[0295] These polymers may also include functional monomer units, functional units, and / or functional groups that provide reactive functional groups for, for example, chemical reactions and bioconjugation reactions. The functional monomer units may be copolymerized or crosslinked with the polymer. All of the emissive polymers described above and in FIG. 3A to FIG. 3N may be physically blended or chemically crosslinked, for example, with one or more emissive and / or absorptive polymers. In some aspects, the polymer may be an energy donor and acceptor, and the emissive polymer may be an energy acceptor. Multistep energy transfer may occur from the absorptive polymer to the luminescent polymer such that the polymer dots provide luminescent emission. Chemical crosslinking between the polymers may use functional reactive groups such as halocarbonyl, hydroxyl, aldehyde, alkenyl, alkynyl, anhydride, formamide, amine, azo compound, carbonate, carboxylate, carboxyl, cyanate, ester, haloalkane, imine, isocyanate, nitrile, nitro, phosphino, phosphate, phosphonate, pyridyl, sulfonyl, sulfonic acid, sulfoxide, thiol group, or any combination thereof. These functional groups may be attached to the side chain and / or the end of each polymer chain.
[0296] Universal monomer unit
[0297] As described herein, the present disclosure may include general monomer units that may be polymerized with the emissive monomer units and / or absorptive monomer units disclosed herein. Figure 4A non-limiting list of exemplary general monomer units (G) is provided. In some embodiments, the general monomer unit can act as an energy donor for the emissive monomer unit. In some embodiments, the general monomer unit can act as an energy acceptor for the absorptive monomer unit. In some embodiments, the general monomer unit can act as a functional monomer unit. A variety of derived monomer units can be used. For example, for Figure 4 the structure shown, R 1 , R 2 , R 3 and R 4 each can independently be selected from, but not limited to, alkyl, phenyl, alkyl-substituted phenyl, alkyl-substituted fluorenyl, and alkyl-substituted carbazolyl. Alkyl-substituted phenyl can include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, and 3,4-dialkylphenyl. Alkyl-substituted fluorenyl can include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. The alkyl substituent can include C n H 2n+1 or C n F 2n+1 or -CH2CH2[OCH2CH2] n -OCH3, where n is from 1 to 20. In some embodiments, n can be between 1 and 50 or higher. The general monomer unit can also be substituted with other substituents as defined herein.
[0298] In certain embodiments, the polymer can include one or more types of general monomer units. As FIG. 5A to FIG. 5E shown, three exemplary types of general monomer units G1, G2, and G2' are shown. Each of the general G1-type monomer units can be copolymerized with each of the G2- and G2'-type monomer units, as well as with the emissive monomer unit and / or the absorptive monomer unit to obtain an emissive polymer, an absorptive monomer unit, and / or an emissive and absorptive polymer. Either the G1-type monomer unit or the G2-type monomer unit can also be used separately to copolymerize with the emissive monomer unit and / or the absorptive monomer unit to obtain an emissive polymer, an absorptive monomer unit, and / or an emissive and absorptive polymer. For Figure 5A the structure shown, a variety of substituents can be attached to the basic structure. For example, R 1 , R 2 , R 3 , R 3 , R 4 , R 5 and R 6Each of which may be independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched-chain alkyl, heteroalkyl, heterocycloalkyl, heterocycloalkylene, alkoxy, aryl, hydroxy, cyano, nitro, ethers and their derivatives, esters and their derivatives, alkyl ketones, alkyl ester alkyl esters, aryl esters, alkynyl, alkyl amines, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl. As an exemplary embodiment, alkyl-substituted phenyl may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyl may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamine-9,9-dialkyl-substituted fluorenyl and 7-diphenylamine-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4”-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl, 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. The alkyl substituent may include C n H2n+1 or C n F 2n+1 or -CH2CH2[OCH2CH2] n -OCH3, where n is from 1 to 20. In some embodiments, n can be between 1 and 50 or higher. The general monomer unit can also be substituted with other substituents as defined herein. As Figure 5A shown, each of X, X 1 and X 2 can independently be selected from carbon (C), silicon (Si), and germanium (Ge). Z, Z 1 , Z 2 can be selected from oxygen (O), sulfur (S), and selenium (Se).
[0299] Figure 5B shows a non-limiting list of general donors in absorbent polymers, emissive polymers, and / or absorbent and emissive polymers. As Figure 5B shown by the chemical structure of the donor, each of X, X 1 , X 2 , X 3 , X 4 , Q, Z, Z 1 and Z 2 can be a heteroatom and can, for example, independently be selected from O, S, Se, Te, N, etc. Each of R 1 and R 2 is independently selected from the following non-limiting examples: hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, heterocycloalkyl, heterocycloalkylene, alkoxy, aryl, hydroxy, cyano, nitro, ethers and their derivatives, esters and their derivatives, alkyl ketones, alkyl ester alkyl esters, aryl esters, alkynyl, alkylamines, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl. As an exemplary embodiment, alkyl-substituted phenyl may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyl may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamine-9,9-dialkyl-substituted fluorenyl and 7-diphenylamine-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4”-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl, 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl.
[0300] In some embodiments, the general donor may be selected from (but not limited to) Figure 5C , Figure 5D and Figure 5E the groups shown. As shown by the various G2 and G2' structures in Figure 5C , Figure 5D and Figure 5E , each of R 1 , R 2 , R 3 and R 4 may independently be selected from the following non-limiting examples: hydrogen (H), deuterium (D), halogen, straight or branched alkyl, heteroalkyl, heterocycloalkyl, heterocycloalkylene, alkoxy, aryl, hydroxy, cyano, nitro, ethers and their derivatives, esters and their derivatives, alkyl ketones, alkyl ester alkyl esters, aryl esters, alkynyl, alkyl amines, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine, and alkyl-substituted thiophenyl. As an exemplary embodiment, alkyl-substituted phenyl may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyl may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamine-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamine-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine, and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl, 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl.
[0301] Characteristics of Narrow-Band Absorption Polymer Dots
[0302] In some embodiments, the chemical composition and structure of the chromogenic polymer in the polymer dots can affect the absorption spectrum of the narrow-band absorbing Pdot. The absorption peak can be shifted from the ultraviolet region to the infrared region. In some embodiments, the absorption peak of the narrow-band absorbing polymer dots can be adjusted to a certain laser wavelength. In some embodiments, for example, the absorption peak can be adjusted to 405 nm. In some embodiments, the absorption peak can be adjusted to about 450 nm. In some embodiments, the absorption peak can be adjusted to about 488 nm. In some embodiments, the absorption peak can be adjusted to about 532 nm. In some embodiments, the absorption peak can be adjusted to about 561 nm. In some embodiments, the absorption peak can be adjusted to about 633 nm. In some embodiments, the absorption peak can be adjusted to about 635 nm. In some embodiments, the absorption peak can be adjusted to about 640 nm. In some embodiments, the absorption peak can be adjusted to about 655 nm. In some embodiments, the absorption peak can be adjusted to about 700 nm. In some embodiments, the absorption peak can be adjusted to about 750 nm. In some embodiments, the absorption peak can be adjusted to about 800 nm. In some embodiments, the absorption peak can be adjusted to about 850 nm. In some embodiments, the absorption peak can be adjusted to about 900 nm. In some embodiments, the absorption peak can be adjusted to about 980 nm. In some embodiments, the absorption peak can be adjusted to the near-infrared region of the wavelength spectrum (e.g., from 750 nm to 1200 nm). In some embodiments, the absorption peak can be adjusted to about 1064 nm. In some embodiments, for example, the absorption peak can be adjusted between 380 nm and 420 nm. In some embodiments, the absorption peak can be adjusted between 440 nm and 460 nm. In some embodiments, the absorption peak can be adjusted between 478 nm and 498 nm. In some embodiments, the absorption peak can be adjusted between 522 nm and 542 nm. In some embodiments, the absorption peak can be adjusted between 550 nm and 570 nm. In some embodiments, the absorption peak can be adjusted between 625 nm and 645 nm. In some embodiments, the absorption peak can be adjusted between 645 nm and 665 nm. In some embodiments, the absorption peak can be adjusted between 690 nm and 710 nm. In some embodiments, the absorption peak can be adjusted between 740 nm and 760 nm. In some embodiments, the absorption peak can be adjusted between 790 nm and 810 nm. In some embodiments, the absorption peak can be adjusted between 890 nm and 910 nm. In some embodiments, the absorption peak can be adjusted between 970 nm and 990 nm. In some embodiments, the absorption peak can be adjusted between 1054 nm and 1074 nm.
[0303] In certain embodiments, the chemical composition and structure of the polymer in the polymer dots can affect the fluorescence quantum yield of the narrow-band absorbing Pdot. For example, the fluorescence quantum yield can vary between 100% and 0.1%. In some embodiments, the quantum yield is greater than 90%. In some embodiments, the quantum yield is greater than 80%. In some embodiments, the quantum yield is greater than 70%. In some embodiments, the quantum yield is greater than 60%. In some embodiments, the quantum yield is greater than 50%. In some embodiments, the quantum yield is greater than 45%. In some embodiments, the quantum yield is greater than 40%. In some embodiments, the quantum yield is greater than 35%. In some embodiments, the quantum yield is greater than 30%. In some embodiments, the quantum yield is greater than 25%. In some embodiments, the quantum yield is greater than 20%. In some embodiments, the quantum yield is greater than 15%. In some embodiments, the quantum yield is greater than 10%. In some embodiments, the quantum yield is greater than 5%. In some embodiments, the quantum yield is greater than 1%.
[0304] The narrow-band absorbing nanoparticles can have an absorption width measured at a percentage value of the absorbance maximum. For example, the absorption width of the nanoparticles at 10% (or in some embodiments, at 15%) of the absorbance maximum can be less than 150 nm.
[0305] In certain embodiments, the nanoparticle absorption width is measured at 20% to 16% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticle at 20% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticle at 19% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticle at 18% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticle at 17% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticle at 16% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticle at 15% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm.In some embodiments, the absorption width of the nanoparticles at 14% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 13% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 12% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 11% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 10% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm.
[0306] In certain embodiments, the absorption width of the nanoparticles is measured at 15% to 11% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 15% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 14% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 13% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 12% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 11% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm.
[0307] In certain embodiments, the absorption width of the nanoparticles is measured at 10% to 6% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 10% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 9% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 8% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 7% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the absorption width of the nanoparticles at 6% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm.
[0308] In certain embodiments, the nanoparticle absorption width is measured at 5% to 1% of the absorbance maximum. In some embodiments, the nanoparticle absorption width at 5% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the nanoparticle absorption width at 4% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the nanoparticle absorption width at 3% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the nanoparticle absorption width at 2% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm. In some embodiments, the nanoparticle absorption width at 1% of the absorbance maximum is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm.
[0309] In certain embodiments, the nanoparticle absorption width is measured at 20% to 16% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 20% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 19% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 18% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm.In some embodiments, the absorption width of the nanoparticles at 17% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 16% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm.
[0310] In certain embodiments, the nanoparticle absorption width is measured at 15% to 11% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 15% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 14% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 13% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm.In some embodiments, the absorption width of the nanoparticles at 12% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 11% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm.
[0311] In certain embodiments, the absorption width of the nanoparticles is measured at 10% to 6% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 10% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 9% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 8% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm.In some embodiments, the absorption width of the nanoparticles at 7% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 6% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm.
[0312] In certain embodiments, the nanoparticle absorption width is measured at 5% to 1% of the absorbance maximum. In some embodiments, the absorption width of the nanoparticles at 5% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 4% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 3% of the absorbance maximum is 10 nm to 200 nm, 50 nm to 200 nm, 80 nm to 100 nm, 100 nm to 200 nm, 120 nm to 200 nm, 150 nm to 200 nm, 10 nm to 150 nm, 50 nm to 150 nm, 80 nm to 150 nm, 90 nm to 150 nm, 100 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, 50 nm to 100 nm, 50 nm to 90 nm, 50 nm to 80 nm, 40 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, or 10 nm to 50 nm.In some embodiments, the absorption width of the nanoparticles at 2% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm. In some embodiments, the absorption width of the nanoparticles at 1% of the absorbance maximum is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm.
[0313] In some embodiments, the absorption width (full width at half maximum, FWHM) at half of the maximum absorbance of the nanoparticles is from 10 nm to 200 nm, from 50 nm to 200 nm, from 80 nm to 100 nm, from 100 nm to 200 nm, from 120 nm to 200 nm, from 150 nm to 200 nm, from 10 nm to 150 nm, from 50 nm to 150 nm, from 80 nm to 150 nm, from 90 nm to 150 nm, from 100 nm to 150 nm, from 50 nm to 140 nm, from 50 nm to 130 nm, from 50 nm to 120 nm, from 50 nm to 110 nm, from 50 nm to 100 nm, from 50 nm to 90 nm, from 50 nm to 80 nm, from 40 nm to 80 nm, from 30 nm to 70 nm, from 30 nm to 60 nm, or from 10 nm to 50 nm. In some embodiments, the absorption width at half of the maximum absorbance of the nanoparticles is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, or less than 30 nm.
[0314] In some embodiments, the narrowband absorbing Pdot may have a secondary absorption peak. In certain embodiments, the secondary absorption peak may be distinguishable from the primary absorption peak (i.e., there is no significant overlap in the absorbance curves). Compared to the primary absorption peak, the secondary absorption peak may have a reduced wavelength value (i.e., the secondary peak wavelength is shorter than the primary absorption peak wavelength). In certain embodiments, the primary absorption peak is the absorption peak having the highest absorbance in the region of 380 nm to 1200 nm. In some embodiments, the secondary absorption peak is in the ultraviolet region. In a particular embodiment, the secondary absorption peak has a wavelength value less than 350 nm. In other particular embodiments, the secondary absorption peak has a wavelength value greater than 380 nm. For example, when an absorbent monomer unit is copolymerized with other absorbent units to produce a narrowband absorbing Pdot, the final Pdot may have a secondary peak due to incomplete absorption of the absorbent monomer unit. In some embodiments, the narrowband absorbing Pdot may also have a secondary peak in a composite Pdot that is chemically crosslinked with a fluorescent dye (e.g., a fluorescent polymer and / or a fluorescent small molecule), a metal complex, etc. In addition to the narrow absorption peak, the secondary peak in the Pdot may be less than 30% of the maximum intensity of the main narrowband absorption. In some embodiments, the secondary peak in the Pdot is less than 25% of the maximum intensity of the main narrowband absorption. In some embodiments, the secondary peak in the Pdot is less than 20% of the maximum intensity of the main narrowband absorption. In some embodiments, the secondary peak in the Pdot is less than 15% of the maximum intensity of the main narrowband absorption. In some embodiments, the secondary peak in the Pdot is less than 10% of the maximum intensity of the main narrowband absorption. In some embodiments, the secondary peak in the Pdot is less than 5% or less of the maximum intensity of the main narrowband absorption.
[0315] In certain embodiments, the emission quality of the polymer dots can be controlled. The emission wavelength of the polymer dots can vary from the ultraviolet to the near-infrared region. The chromogenic polymer dots include at least one chromogenic polymer. As provided herein, the chemical composition and structure of the polymer can be adjusted to obtain a small bandwidth (FWHM) of the Pdot emission. Other species such as narrow-band emission units, metal complexes, or inorganic materials can be blended or chemically cross-linked within the chromogenic polymer dots to obtain a small bandwidth (FWHM) of the Pdot emission. In some embodiments, the FWHM is less than about 100 nm. In some embodiments, the FWHM is less than about 90 nm. In some embodiments, the FWHM is less than about 80 nm. In some embodiments, the FWHM is less than about 70 nm. In some embodiments, the FWHM is less than about 65 nm. In some embodiments, the FWHM is less than about 60 nm. In some embodiments, the FWHM is less than about 55 nm. In some embodiments, the FWHM is less than about 50 nm. In some embodiments, the FWHM is less than about 45 nm. In some embodiments, the FWHM is less than about 40 nm. In some embodiments, the FWHM is less than about 35 nm. In some embodiments, the FWHM is less than about 30 nm. In some embodiments, the FWHM is less than about 25 nm. In certain embodiments, the FWHM is less than about 24 nm, 23 nm, 22 nm, 21 nm, 20 nm, 19 nm, 18 nm, 17 nm, 16 nm, 15 nm, 14 nm, 13 nm, 12 nm, 11 nm, 10 nm or less. In some embodiments, the FWHM of the polymer dots described herein can be in the range of about 5 nm to about 70 nm, about 10 nm to about 60 nm, about 20 nm to about 50 nm, or about 30 nm to about 45 nm.
[0316] In certain embodiments, the chemical composition and structure of the polymer in the polymer dots can affect the fluorescence lifetime of the narrow-band absorbing Pdot. The fluorescence lifetime can vary between 10 ps and 1 ms. In some embodiments, the fluorescence lifetime varies between 10 ps and 100 ps. In some embodiments, the fluorescence lifetime varies between 100 ps and 1 ns. In some embodiments, the fluorescence lifetime varies between 1 ns and 10 ns. In some embodiments, the fluorescence lifetime varies between 10 ns and 100 ns. In some embodiments, the fluorescence lifetime varies between 100 ns and 1 μs. In some embodiments, the fluorescence lifetime varies between 1 μs and 10 μs. In some embodiments, the fluorescence lifetime varies between 10 μs and 100 μs. In some embodiments, the fluorescence lifetime varies between 100 μs and 1 ms.
[0317] In certain embodiments, narrowband-absorbing Pdots can be characterized by their stability. Optical properties (e.g., absorption spectrum, absorption bandwidth, absorption peak, emission spectrum, emission bandwidth, fluorescence quantum yield, fluorescence lifetime, side peaks, brightness at a specific wavelength, or emission intensity at a specific wavelength) can be stable for more than 1 day or 1 week or 2 weeks or 1 month or 2 months or 3 months or 6 months or 1 year or longer. A stable fluorescence quantum yield means that the change in the fluorescence quantum yield of the emission does not exceed 5%, 10%, 20%, 50%, or more. A stable absorption spectrum means that the change in the width of the main peak does not exceed 5%, 10%, or 20%. A stable emission spectrum means that the change in the width of the main peak does not exceed 5%, 10%, or 20%.
[0318] In some embodiments, the hydrodynamic diameter of the narrowband-absorbing nanoparticles is less than 1000 nm, less than 900 nm, less than 800 nm, less than 700 nm, less than 600 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 150 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, or less than 10 nm, as measured by dynamic light scattering. In some aspects, the critical size of the narrowband-absorbing nanoparticles is greater than 3 nm and less than 1000 nm, greater than 10 nm and less than 1000 nm, greater than 20 nm and less than 1000 nm, greater than 30 nm and less than 1000 nm, greater than 40 nm and less than 1000 nm, greater than 50 nm and less than 1000 nm, greater than 3 nm and less than 100 nm, greater than 3 nm and less than 90 nm, greater than 3 nm and less than 80 nm, greater than 3 nm and less than 70 nm, greater than 3 nm and less than 60 nm, greater than 3 nm and less than 50 nm, greater than 3 nm and less than 40 nm, greater than 3 nm and less than 30 nm, greater than 3 nm and less than 20 nm, or greater than 3 nm and less than 10 nm.
[0319] In some embodiments, the quantum yield of the narrowband absorbent nanoparticles is greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90% or greater than 95%. In certain embodiments, the quantum yield of the narrowband absorbent nanoparticles is from 0.10 to 1.00, 0.10 to 0.90, 0.10 to 0.75, 0.10 to 0.50, 0.25 to 1.00, 0.25 to 0.90, 0.25 to 0.75, 0.25 to 0.50, 0.50 to 1.00, 0.50 to 0.90 or 0.50 to 0.75. In some embodiments, the quantum yield of the narrowband absorbent nanoparticles is greater than 0.1, greater than 0.2, greater than 0.3, greater than 0.4, greater than 0.5, greater than 0.6, greater than 0.7, greater than 0.8 or greater than 0.9. In certain embodiments, the quantum yield is measured between 400 nm and 900 nm.
[0320] In certain embodiments, a low mass percentage of the absorbent monomer units in the narrowband absorbent nanoparticles is beneficial. In some embodiments, the absorbent monomer units are less than 50% of the total mass of the nanoparticles, less than 40% of the total mass of the nanoparticles, less than 30% of the total mass of the nanoparticles, less than 25% of the total mass of the nanoparticles, less than 20% of the total mass of the nanoparticles, less than 15% of the total mass of the nanoparticles, less than 14% of the total mass of the nanoparticles, less than 13% of the total mass of the nanoparticles, less than 12% of the total mass of the nanoparticles, less than 11% of the total mass of the nanoparticles, less than 10% of the total mass of the nanoparticles, less than 9% of the total mass of the nanoparticles, less than 8% of the total mass of the nanoparticles, less than 7% of the total mass of the nanoparticles, less than 6% of the total mass of the nanoparticles, less than 5% of the total mass of the nanoparticles, less than 4% of the total mass of the nanoparticles, less than 3% of the total mass of the nanoparticles, less than 2% of the total mass of the nanoparticles or less than 1% of the total mass of the nanoparticles.
[0321] In other embodiments, a high mass percentage of the absorptive monomer units in the narrowband absorptive nanoparticles is beneficial. In some embodiments, the absorptive monomer units are greater than 1%, greater than 2%, greater than 3%, greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 11%, greater than 12%, greater than 13%, greater than 14%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, or greater than 70% of the total mass of the nanoparticles.
[0322] In some embodiments, the emissive monomer units emit chemiluminescence after absorbing energy, which excites electrons within the monomer units and results in the emission of photons of light. In certain embodiments, the energy is from intra-chain or inter-chain energy transfer. For example, the absorptive monomer units can be excited by external emission (e.g., a laser beam); the excited absorptive monomer units can then transfer the energy intra-chain to a common monomer unit, inter-chain to a common monomer unit, intra-chain to an emissive monomer unit, and / or inter-chain to an emissive monomer unit. The common monomer unit can further transfer the energy intra-chain or inter-chain to the emissive monomer unit. In certain embodiments, the energy transfer includes FRET. In some embodiments, the energy transfer includes inter-chain energy transfer. In certain embodiments, the energy transfer includes cross-bond energy transfer.
[0323] In some embodiments, it is advantageous for the ratio of the number of absorptive monomer units in the narrowband absorptive monomer units to be low compared to the number of emissive monomer units. Without being limited to a particular theory or concept, a large number of emissive monomer units can provide increased brightness and can allow for better signal recognition or interpretation (e.g., if the absorptive monomer units and / or the common monomer units are particularly efficient in absorption and / or energy transfer, an excessive number of emissive monomer units can provide several distinguishable luminescent signals, or a stronger single signal). As a non-limiting example, the ratio of absorptive monomer units to emissive monomer units in a narrowband absorptive monomer unit including 3 absorptive monomer units and 15 emissive monomer units is 1:5. In certain embodiments, the ratio of absorptive monomer units to emissive monomer units in the narrowband absorptive nanoparticles is less than 1:1, less than 1:2, less than 1:3, less than 1:4, less than 1:5, less than 1:6, less than 1:7, less than 1:8, less than 1:9, less than 1:10, less than 1:11, less than 1:12, less than 1:13, less than 1:14, less than 1:15, less than 1:16, less than 1:17, less than 1:18, less than 1:19, less than 1:20, less than 1:25, less than 1:30, less than 1:35, less than 1:40, less than 1:50, less than 1:60, less than 1:70, less than 1:80, less than 1:90, or less than 1:100.
[0324] In other embodiments, it is advantageous for the ratio of the number of absorptive monomer units in the narrowband absorptive monomer units to be high compared to the number of emissive monomer units. Without being limited to a particular theory or concept, a large number of absorptive monomer units can improve brightness by increasing the absorption cross-section and can allow for better signal recognition or interpretation (e.g., if the absorptive monomer units and / or the common monomer units are not efficient in absorption and / or energy transfer, an excessive number of absorptive monomer units can improve the luminescent signal by increasing the number of excitation points within the nanoparticles). As a non-limiting example, the ratio of absorptive monomer units to emissive monomer units in a narrowband absorptive monomer unit including 15 absorptive monomer units and 3 emissive monomer units is 5:1. In certain embodiments, the ratio of absorptive monomer units to emissive monomer units in the narrowband absorptive nanoparticles is greater than 1:1, greater than 2:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1, greater than 8:1, greater than 9:1, greater than 10:1, greater than 11:1, greater than 12:1, greater than 13:1, greater than 14:1, greater than 15:1, greater than 16:1, greater than 17:1, greater than 18:1, greater than 19:1, greater than 20:1, greater than 25:1, greater than 30:1, greater than 35:1, greater than 40:1, greater than 50:1, greater than 60:1, greater than 70:1, greater than 80:1, greater than 90:1, or greater than 100:1.
[0325] In certain embodiments, the narrowband absorptive nanoparticles emit a bright signal, the brightness of which can be calculated as the product of the quantum yield and the absorption cross-section. In some embodiments, the brightness of the narrowband absorptive nanoparticles is greater than 1.0×10 -16 cm 2 、 greater than 1.0×10 -15 cm 2 、 greater than 1.0×10 -14 cm 2 、 greater than 1.0×10 -13 cm 2 、 greater than 1.0×10 -12 cm 2 、 greater than 1.0×10 -11 cm 2 、 greater than 1.0×10 -10 cm 2 、 greater than 1.0×10 -9 cm 2 、 greater than 1.0×10 -8 cm 2 、 greater than 1.0×10 -7 cm 2 、 greater than 1.0×10 -6 cm 2 、 greater than 1.0×10 -5 cm 2 or greater than 1.0×10 -4 cm 2 。
[0326] In some embodiments, the brightness of the narrowband absorptive nanoparticles is greater than 1.0×10 -13 cm 2 、 greater than 2.0×10 -13 cm 2 、 greater than 3.0×10 -13 cm 2 、 greater than 4.0×10 -13 cm 2 、 greater than 5.0×10 -13 cm 2 、 greater than 6.0×10 -13 cm 2 、 greater than 7.0×10 -13 cm 2 、 greater than 8.0×10 -13 cm 2 、 greater than 9.0×10 -13 cm 2 、 greater than 1.0×10 -12 cm 2 、 greater than 2.0×10- 12 cm 2 and greater than 3.0×10 -12 cm 2 and greater than 4.0×10 -12 cm 2 and greater than 5.0×10 -12 cm 2 and greater than 6.0×10 -12 cm 2 and greater than 7.0×10 -12 cm 2 and greater than 8.0×10 -12 cm 2 and greater than 9.0×10 -12 cm 2 and greater than 1.0×10 -11 cm 2 and greater than 2.0×10 - 11 cm 2 and greater than 3.0×10 -11 cm 2 and greater than 4.0×10 -11 cm 2 and greater than 5.0×10 -11 cm 2 and greater than 6.0×10 -11 cm 2 and greater than 7.0×10 -11 cm 2 and greater than 8.0×10 -11 cm 2 or greater than 9.0×10 -11 cm 2 In some embodiments, the brightness of the narrowband absorbing nanoparticles is from 1.0×10 -14 cm 2 to 1.0×10 -13 cm 2 In some embodiments, the brightness of the narrowband absorbing nanoparticles is from 1.0×10 -13 cm 2 to 1.0×10 -12 cm 2 In some embodiments, the brightness of the narrowband absorbing nanoparticles is from 1.0×10 -12 cm 2 to 1.0×10 -11 cm 2 .
[0327] In some embodiments, the narrowband absorbing nanoparticles have a high brightness, which is calculated as the product of the emission quantum yield and the absorption cross section (i.e., brightness = ФPL × σ). In some embodiments, the brightness is greater than 1.0×10 -15 cm 2 、 greater than 1.0×10 -14 cm 2 、 greater than 1.0×10 -13 cm 2 、 greater than 1.0×10 -12 cm 2 、 greater than 1.0×10 -11 cm 2 、 greater than 1.0×10 -10 cm 2 or greater than 1.0×10 -9 cm 2 。 In certain embodiments, the brightness is 1.0×10 -15 cm 2 to 1.0×10 -9 cm 2 。 In certain embodiments, the brightness is 1.0×10 -14 cm 2 to 1.0×10 -10 cm 2 。 In certain embodiments, the brightness is 1.0×10 -14 cm 2 to 1.0×10 -11 cm 2 。 In certain embodiments, the brightness is 1.0×10 -14 cm 2 to 1.0×10 -12 cm 2 。 In certain embodiments, the brightness is 1.0×10 -13 cm 2 to 1.0×10 -12 cm 2 。 In certain embodiments, the brightness is 1.0×10 -15 cm 2 to 1.0×10 -14 cm 2 。 In certain embodiments, the brightness is 1.0×10 -14 cm 2 to 1.0×10 -13 cm 2 。 In certain embodiments, the brightness is 1.0×10 -13 cm 2 to 1.0×10 -12 cm 2 。 In certain embodiments, the brightness is 1.0×10 -12 cm 2 to 1.0×10- 11 cm 2 For example, the polymeric nanoparticles can have a brightness of 2.0×10 -13 cm 2 .
[0328] In certain embodiments, the narrowband absorptive nanoparticles include at least one characteristic selected from each of (a), (b), and (c):
[0329] (a) an absorption width at 10% (or in some embodiments, at 15%) of the absorbance maximum that is less than 200 nm, less than 190 nm, less than 180 nm, less than 170 nm, less than 160 nm, less than 150 nm, less than 140 nm, less than 130 nm, less than 120 nm, less than 110 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, or less than 40 nm;
[0330] (b) a quantum yield that is greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95%; and
[0331] (c) a brightness that is greater than 1.0×10 -16 cm 2 , greater than 1.0×10 -15 cm 2 , greater than 1.0×10 -14 cm 2 , greater than 1.0×10 -13 cm 2 , greater than 1.0×10 -12 cm 2 , greater than 1.0×10 -11 cm 2 , greater than 1.0×10 -10 cm 2 , greater than 1.0×10 -9 cm 2 , greater than 1.0×10 -8 cm 2 , greater than 1.0×10 -7 cm 2 , greater than 1.0×10 -6 cm 2 , greater than 1.0×10 -5 cm 2 or greater than 1.0×10 -4 cm 2 。
[0332] In some embodiments, emissive polymers (i.e., polymers comprising emissive monomer units) can exhibit broadband emission in good solvents, such as some hydrophobic polymers in tetrahydrofuran solution. However, after these polymers are formed into Pdot nanoparticles in water, the nanoparticles exhibit narrowband emission. In good solvents, hydrophobic semiconductor polymers generally adopt an extended rod-like conformation, and the interchain energy transfer efficiency is not high. When the polymers are densely packed into tight nanoparticles, the resulting Pdot has narrowband emission because the intra-particle energy transfer and interchain energy transfer are much more efficient in the nanoparticle form.
[0333] In some embodiments, emissive polymers (i.e., polymers comprising emissive monomer units) can have narrow emission in good solvents, such as some hydrophobic polymers in toluene solution. However, after these polymers are formed into nanoparticles in water using the nanoprecipitation method, the Pdot exhibits broad emission due to complex backbone folding behavior, disordered morphology, and chain aggregation. Pdot can be prepared using the miniemulsion method, which can maintain the narrow emission of the polymer.
[0334] In certain embodiments, narrowband absorbent nanoparticles have a high energy transfer efficiency. In some embodiments, as further disclosed herein, the energy transfer efficiency can be estimated. In some embodiments, the estimated energy transfer efficiency from the absorbent polymer to the emissive polymer is greater than 99%, greater than 98%, greater than 97%, greater than 96%, greater than 95%, greater than 94%, greater than 93%, greater than 92%, greater than 91%, greater than 90%, greater than 89%, greater than 88%, greater than 87%, greater than 86%, greater than 85%, greater than 84%, greater than 83%, greater than 82%, greater than 81%, greater than 80%, greater than 75%, greater than 70%, greater than 65%, greater than 60%, greater than 55%, or greater than 50%. In some embodiments, the estimated energy transfer efficiency from the absorbent monomer unit to the emissive monomer unit is greater than 99%, greater than 98%, greater than 97%, greater than 96%, greater than 95%, greater than 94%, greater than 93%, greater than 92%, greater than 91%, greater than 90%, greater than 89%, greater than 88%, greater than 87%, greater than 86%, greater than 85%, greater than 84%, greater than 83%, greater than 82%, greater than 81%, greater than 80%, greater than 75%, greater than 70%, greater than 65%, greater than 60%, greater than 55%, or greater than 50%.
[0335] In some embodiments, the narrowband absorptive nanoparticles have a high molar attenuation coefficient (i.e., molar extinction coefficient, molar absorptivity). The molar attenuation coefficient is a measure of the intensity of light at a given wavelength attenuated by the nanoparticles. In certain embodiments, the molar attenuation coefficient is measured at 380 nm, 405 nm, 450 nm, 488 nm, 532 nm, 561 nm, 633 nm, 640 nm, 655 nm, 700 nm, 750 nm, 800 nm, 900 nm, 980 nm, or 1064 nm. In some embodiments, the molar attenuation coefficient is measured at values from 380 nm to 1200 nm. In certain embodiments, the molar attenuation coefficient can be greater than 1.0×10 5 M -1 cm -1 、 greater than 1.0×10 6 M -1 cm -1 、 greater than 1.0×10 7 M -1 cm -1 、 greater than 1.0×10 8 M -1 cm -1 、 greater than 1.0×10 9 M -1 cm -1 or greater than 1.0×10 10 M -1 cm -1 。 In some embodiments, the molar attenuation coefficient can be 1.0×10 5 M -1 cm -1 to 1.0×10 6 M -1 cm -1 。 In some embodiments, the molar attenuation coefficient can be 1.0×10 6 M -1 cm -1 to 1.0×10 7 M -1 cm -1 。 In some embodiments, the molar attenuation coefficient can be 1.0×10 7 M -1 cm -1 to 1.0×10 8 M -1 cm -1 。 In some embodiments, the molar attenuation coefficient can be 1.0×10 8 M -1 cm -1 to 1.0×10 9 M -1 cm -1。As a non-limiting example, the molar extinction coefficient of the polymer nanoparticles can be measured at 532 nm and provided with a value of 2.0×10 8 M -1 cm -1 .
[0336] In certain embodiments, the narrowband absorbent nanoparticles have a high cross-sectional absorbance (also referred to herein as "absorption cross-section"). The cross-sectional absorbance can be denoted by "σ". In certain embodiments, the cross-sectional absorbance is measured at 380 nm, 405 nm, 450 nm, 488 nm, 532 nm, 561 nm, 633 nm, 640 nm, 655 nm, 700 nm, 750 nm, 800 nm, 900 nm, 980 nm, or 1064 nm. In some embodiments, the absorption cross-section is greater than 1.0×10 -15 cm 2 , greater than 1.0×10 -14 cm 2 , greater than 1.0×10 -13 cm 2 , greater than 1.0×10 -12 cm 2 , greater than 1.0×10 -11 cm 2 , or greater than 1.0×10 -10 cm 2 . In some embodiments, the absorption cross-section is from 1.0×10 -15 cm 2 to 1.0×10 -14 cm 2 . In some embodiments, the absorption cross-section is from 1.0×10 -14 cm 2 to 1.0×10 -13 cm 2 . In some embodiments, the absorption cross-section is from 1.0×10 -13 cm 2 to 1.0×10 -12 cm 2 . In some embodiments, the absorption cross-section is from 1.0×10 -12 cm 2 to 1.0×10 -11 cm 2 . In some embodiments, the absorption cross-section is from 1.0×10 -11 cm 2 to 1.0×10 -10 cm 2 . In certain embodiments, the absorption cross-section is greater than 5.0×10 -14 cm 2 , greater than 1.0×10- 13 cm 2 、 greater than 2.0×10 -13 cm 2 、 greater than 3.0×10 -13 cm 2 、 greater than 4.0×10 -13 cm 2 、 greater than 5.0×10 -13 cm 2 、 greater than 6.0×10 -13 cm 2 、 greater than 7.0×10 -13 cm 2 、 greater than 8.0×10 -13 cm 2 、 greater than 9.0×10 -13 cm 2 、 greater than 1.0×10 - 12 cm 2 、 greater than 2.0×10 -12 cm 2 、 greater than 3.0×10 -12 cm 2 、 greater than 4.0×10 -12 cm 2 、 greater than 5.0×10 -12 cm 2 、 greater than 6.0×10 -12 cm 2 、 greater than 7.0×10 -12 cm 2 、 greater than 8.0×10 -12 cm 2 、 greater than 9.0×10 -12 cm 2 、 greater than 1.0×10 - 11 cm 2 、 greater than 2.0×10 -11 cm 2 、 greater than 3.0×10 -11 cm 2 、 greater than 4.0×10 -11 cm 2 、 greater than 5.0×10 -11 cm 2 、 greater than 6.0×10 -11 cm 2 、 greater than 7.0×10 -11 cm 2 、 greater than 8.0×10 -11 cm 2 or greater than 9.0×10-11 cm 2 As a non-limiting example, the absorption cross-section of the nanoparticles can be measured at 532 nm (σ 532nm ), and has a value of 1.0×10 -12 cm 2 .
[0337] In certain embodiments, the narrowband absorptive nanoparticles have a high brightness per volume of nanoparticles. The brightness per volume can be calculated by dividing the brightness value by the volume of the nanoparticles (i.e., brightness per volume = (Ф PL ×σ) / V). In some embodiments, the brightness per volume is greater than 3,000 cm -1 , greater than 4,000 cm -1 , greater than 5,000 cm -1 , greater than 6,000 cm -1 , greater than 7,000 cm -1 , greater than 8,000 cm -1 , greater than 9,000 cm -1 , greater than 10,000 cm -1 , greater than 11,000 cm -1 , greater than 12,000 cm -1 , greater than 13,000 cm -1 , greater than 14,000 cm -1 , greater than 15,000 cm -1 , greater than 16,000 cm -1 , greater than 17,000 cm -1 , greater than 18,000 cm -1 , greater than 19,000 cm -1 , greater than 20,000 cm -1 , greater than 25,000 cm -1 , greater than 30,000 cm -1 , greater than 35,000 cm -1 , greater than 40,000 cm -1 , greater than 45,000 cm -1 , greater than 50,000 cm -1 , greater than 60,000 cm -1 , greater than 70,000 cm -1 , greater than 80,000 cm -1 , greater than 90,000 cm -1 , greater than 100,000 cm -1 , greater than 250,000 cm -1 , greater than 500,000 cm -1 or greater than 1,000,000 cm-1 In certain embodiments, the brightness per volume of the nanoparticles is 5,000 cm -1 to 100,000 cm -1 In certain embodiments, the brightness per volume of the nanoparticles is 10,000 cm -1 to 90,000 cm -1 In certain embodiments, the brightness per volume of the nanoparticles is 20,000 cm -1 to 80,000 cm -1 In certain embodiments, the brightness per volume of the nanoparticles is 30,000 cm -1 to 70,000 cm -1 In certain embodiments, the brightness per volume of the nanoparticles is 30,000 cm -1 to 60,000 cm -1 In certain embodiments, the brightness per volume of the nanoparticles is 30,000 cm -1 to 50,000 cm -1 For example, the polymeric nanoparticles can have a brightness per volume of 40,000 cm -1 .
[0338] Compositions of narrow-band absorbing polymer dots
[0339] As further described herein, the present disclosure includes a variety of polymeric nanoparticles that exhibit narrowband absorption characteristics and additionally exhibit emission characteristics. The polymeric nanoparticles can include an absorptive polymer, an emissive polymer, an absorptive and emissive polymer, or any combination thereof. As further described herein, the various polymer dots of the present disclosure can include a polymer having an emissive unit (e.g., an emissive monomer unit and / or an emissive unit). For example, the present disclosure can include a heteropolymer that includes an emissive monomer unit such as BODIPY, a BODIPY derivative, squaric acid, a squaric acid derivative, or any combination thereof. The present disclosure can include a heteropolymer that includes an emissive unit such as a metal complex and / or a metal complex derivative monomer unit, a porphyrin and / or a porphyrin derivative monomer unit, a phthalocyanine and / or a phthalocyanine derivative monomer unit, a lanthanide complex and / or a lanthanide complex derivative monomer unit, a perylene and / or a perylene derivative monomer unit, a cyanine and / or a cyanine derivative monomer unit, a rhodamine and / or a rhodamine derivative monomer unit, a coumarin and / or a coumarin derivative monomer unit, and / or an oxazine and / or an oxazine derivative monomer unit. The emissive unit can be, for example, an emissive monomer unit or a fluorescent nanoparticle embedded or attached to the polymer dot. The fluorescent nanoparticle can be, for example, a quantum dot. The emissive unit can also include a polymer or a fluorescent dye molecule that provides emission in the polymer dots of the present disclosure.
[0340] As further described herein, the present disclosure includes a variety of polymer dots that exhibit absorption characteristics. As further described herein, the various polymer dots of the present disclosure may include polymers having absorption units (e.g., absorbent monomer units and / or absorbent units). For example, the present disclosure may include heteropolymers that include absorbent monomer units such as BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof. The present disclosure may include heteropolymers that include absorbent units such as metal complex and / or metal complex derivative monomer units, porphyrin and / or porphyrin derivative monomer units, phthalocyanine and / or phthalocyanine derivative monomer units, perylene and / or perylene derivative monomer units, cyanine and / or cyanine derivative monomer units, rhodamine and / or rhodamine derivative monomer units, coumarin and / or coumarin derivative monomer units, and / or xanthene and / or xanthene derivative monomer units. The absorbent units may also include polymers or fluorescent dye molecules that provide absorption in the polymer dots of the present disclosure. In certain embodiments, the absorbent monomer units are narrow-band absorbent monomer units.
[0341] The absorbent monomer units may be incorporated into heteropolymers with other common monomer units that can, for example, act as energy donors. For example, the common monomer units may include an absorption spectrum that is tuned to substantially overlap with the emission spectrum of the narrow-band absorbent monomer units, thereby acting as an energy acceptor for the narrow-band absorbent monomer units. As another example, the common monomer units may include an emission spectrum that is tuned to substantially overlap with the absorption spectrum of the emissive monomer units, thereby acting as an energy donor for the emissive monomer units. Energy transfer may occur, for example, along the polymer backbone (e.g., intra-chain) or between multiple polymer backbones (e.g., inter-chain). In some embodiments, the absorbent units may be linked (e.g., covalently linked) to the polymer backbone or a side chain of the polymer. For example, the absorbent units may be linked to common monomer units that may include an absorption spectrum that is tuned to substantially overlap with the emission spectrum of the narrow-band absorbent units, thereby acting as an energy acceptor for the narrow-band absorbent units.
[0342] In some embodiments, the absorbent monomer units can be incorporated into a heteropolymer having energy transfer monomer units. In certain embodiments, the narrowband absorbent nanoparticles include energy transfer monomer units. The energy transfer monomer units can have a large Stokes shift (i.e., the difference between the absorption peak and the emission peak band maxima). In certain embodiments, the energy transfer monomer units have a Stokes shift greater than 30 nm, greater than 40 nm, greater than 50 nm, greater than 60 nm, greater than 70 nm, greater than 80 nm, greater than 90 nm, greater than 100 nm, greater than 110 nm, greater than 120 nm, greater than 130 nm, greater than 140 nm, greater than 150 nm, greater than 175 nm, greater than 200 nm, greater than 225 nm, greater than 250 nm, greater than 275 nm, greater than 300 nm, greater than 320 nm, greater than 350 nm, greater than 375 nm, or greater than 400 nm. In some embodiments, the energy transfer monomer units have a Stokes shift of 20 nm to 250 nm, 30 nm to 200 nm, 30 nm to 175 nm, 30 nm to 150 nm, 30 nm to 140 nm, 30 nm to 130 nm, 30 nm to 120 nm, 30 nm to 110 nm, 30 nm to 100 nm, 40 nm to 200 nm, 40 nm to 175 nm, 40 nm to 150 nm, 40 nm to 140 nm, 40 nm to 130 nm, 40 nm to 120 nm, 40 nm to 110 nm, 40 nm to 100 nm, 50 nm to 200 nm, 50 nm to 175 nm, 50 nm to 150 nm, 50 nm to 140 nm, 50 nm to 130 nm, 50 nm to 120 nm, 50 nm to 110 nm, or 50 nm to 100 nm. In certain embodiments, the energy transfer monomer units can be the general monomer units as described herein.
[0343] The general monomer units can include a variety of structures further described herein (e.g., G1, G2, G2'). In some embodiments, the general monomer units can include, for example, fluorene, fluorene derivatives, phenylvinylenes, phenylvinylene derivatives, phenylene, phenylene derivatives, benzothiazoles, benzothiazole derivatives, thiophenes, thiophene derivatives, carbazole fluorene, and / or carbazole fluorene derivatives. Also as described herein, the various polymers used in polymer dots can be combined in a variety of ways. For example, the polymers of the present disclosure can be chemically crosslinked and / or physically blended in the polymer dots. The polymers described herein can also include at least one functional group for, for example, conjugation reactions, such as bioconjugation reactions with antibodies or other biomolecules further described herein. The present disclosure further includes compositions containing the polymer dots described herein. The compositions of the present disclosure can include, for example, the polymer dots described herein suspended in a solvent (e.g., an aqueous solution).
[0344] In some embodiments, the narrow-band absorbing polymer dots comprise at least one narrow-band absorbing polymer. The narrow-band absorbing polymer can be a homopolymer or a heteropolymer (e.g., a copolymer). The narrow-band absorbing polymer can have broadband absorption in a solvent. However, the final Pdot made from the narrow-band absorbing polymer has narrow-band absorption.
[0345] In certain embodiments, the polymer dots can comprise a luminescent semiconductor polymer having delocalized π electrons. The term "semiconductor polymer" is well recognized in the art. Conventional luminescent semiconductor polymers include, but are not limited to, fluorene polymers, phenylene vinylene polymers, phenylene polymers, benzothiadiazole polymers, thiophene polymers, carbazole polymers, and related copolymers. Although conventional semiconductor polymers generally have broadband absorption, the narrow-band absorbing polymer includes chemical units such as narrow-band absorbing monomer units such that the final Pdot provides narrow-band absorption.
[0346] In some embodiments, the narrow-band absorbing polymer used to prepare the Pdot comprises narrow-band absorbing monomer units. The narrow-band absorbing polymer dots can also comprise other monomer units that are broadband absorbing. The narrow-band absorbing monomer units can be energy acceptors, and the other monomer units can be energy donors. The narrow-band absorbing monomer units can be energy donors, and the other monomer units can be energy acceptors. For example, the polymer dots of the present disclosure can comprise condensed polymer nanoparticles having intramolecular energy transfer between, for example, narrow-band absorbing monomer units and one or more common monomer units on the same polymer chain. The polymer dots can also have intermolecular energy transfer, where the condensed polymer nanoparticles can comprise two or more polymer chains physically blended and / or chemically crosslinked together. For intermolecular energy transfer, one chain can comprise narrow-band absorbing monomer units, and the other chain can comprise one or more common monomer units that can act as an energy acceptor for the narrow-band absorbing monomer units, which are energy donors. Some polymer dots can comprise both intramolecular and intermolecular energy transfer. In some cases, a combination of intramolecular and intermolecular energy transfer can increase the quantum yield of the polymer dots. In some embodiments, the narrow-band absorbing Pdot is narrow-band absorbing and does not rely on the formation of any defined secondary structure.
[0347] The compounds of the present disclosure can be prepared in a variety of ways known to those skilled in the art of organic synthesis. The compounds of the present disclosure can be synthesized using the methods described below, together with synthetic methods known in the art of synthetic organic chemistry or variations of the methods understandable to those skilled in the art.
[0348] The compounds of the present disclosure can be prepared from readily available starting materials using the following general methods and procedures. It should be understood that typical or preferred process conditions (i.e., reaction temperature, time, molar ratio of reactants, solvent, pressure, etc.) are given; other process conditions can also be used unless otherwise stated. The optimal reaction conditions can vary depending on the specific reactants or solvents used, but such conditions can be determined by those skilled in the art through routine optimization procedures.
[0349] The processes described herein can be monitored according to any suitable method known in the art. For example, by spectroscopic means such as nuclear magnetic resonance spectroscopy (e.g., 1 H or 13 C), infrared spectroscopy, spectrophotometry (e.g., UV-visible), or mass spectrometry; or by chromatography such as high performance liquid chromatography (HPLC) or thin layer chromatography to monitor the formation of the product. The compounds obtained by the reaction can be purified by any suitable method known in the art. For example, chromatography (medium pressure) HPLC on a suitable adsorbent (e.g., silica gel, alumina, etc.), or preparative thin layer chromatography; distillation; sublimation, trituration, or recrystallization.
[0350] The preparation of the compounds may involve the protection and deprotection of various chemical groups. The need for protection and deprotection and the selection of appropriate protecting groups can be readily determined by those skilled in the art. The chemistry of protecting groups can be found, for example, in Wuts and Greene, Greene's Protective Groups in Organic Synthesis, 4th Edition, John Wiley & Sons: New York, 2006, which is incorporated herein by reference in its entirety.
[0351] The reactions of the processes described herein can be carried out in a suitable solvent that can be readily selected by one of ordinary skill in the art of organic synthesis. The suitable solvent is substantially non-reactive with the starting materials (reactants), intermediates, or products at the temperature at which the reaction is carried out (i.e., a temperature within the range from the freezing temperature to the boiling temperature of the solvent). A given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the reaction step, a suitable solvent for that particular reaction step can be selected. Suitable solvents include water, alkanes (such as pentane, hexane, heptane, cyclohexane, etc., or mixtures thereof), aromatic solvents (such as benzene, toluene, xylene, etc.), alcohols (such as methanol, ethanol, isopropyl alcohol, etc.), ethers (such as dialkyl ethers, methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), dioxane, etc.), esters (such as ethyl acetate, butyl acetate, etc.), halogenated solvents (such as dichloromethane (DCM), chloroform, dichloroethane, tetrachloroethane), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, acetonitrile (ACN), hexamethylphosphoramide (HMPA), and N-methylpyrrolidone (NMP). These solvents can be used in their wet or anhydrous forms.
[0352] The resolution of a racemic mixture of a compound can be carried out by any of a variety of methods known in the art. Exemplary methods include fractional recrystallization using a "chiral resolving acid", which is an optically active salt-forming organic acid. Suitable resolving agents for the fractional recrystallization method are, for example, optically active acids such as D- and L-forms of tartaric acid, diacetyltartaric acid, dibenzoyltartaric acid, mandelic acid, malic acid, lactic acid, or various optically active camphorsulfonic acids. The resolution of the racemic mixture can also be carried out by elution on a column packed with an optically active resolving agent (e.g., dinitrobenzoyl phenylglycine). The appropriate elution solvent composition can be determined by one of ordinary skill in the art.
[0353] The compounds of the present disclosure can be prepared, for example, using the reaction pathways and techniques (including the figures) described in the present disclosure.
[0354] As will be understood by one of ordinary skill in the art, the various chemical terms defined herein can be used to describe the chemical structures of the polymers and monomer units of the present disclosure. For example, various monomer unit derivatives (e.g., BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof) can include the various chemical substituents and groups described herein. For example, in some embodiments, derivatives of the various monomer units can be substituted with hydrogen, deuterium, alkyl, alkyl-aryl, aryl, alkoxy-aryl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, N-dialkoxyphenyl-4-phenyl, amino, sulfide, aldehyde, ester, ether, acid, and / or hydroxyl.
[0355] BODIPY and various BODIPY derivatives can be used in the present disclosure. BODIPY and BODIPY derivatives can polymerize to form polymers (e.g., homopolymers or heteropolymers) and / or can be linked (e.g., covalently linked) to the polymer backbone, side chains, and / or termini. BODIPY monomer units and their derivatives include, but are not limited to, their alkyl derivatives, aryl derivatives, alkyne derivatives, aromatic derivatives, alkoxide derivatives, aza derivatives, BODIPY extended systems, and other BODIPY derivatives. In some embodiments, the polymer dots of the present disclosure can include a polymer that includes an absorptive monomer unit (e.g., a narrow-band absorptive monomer unit) and / or an emissive monomer unit having the following formula:
[0356]
[0357] wherein the variables R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A and R 4B each variable or two variables on adjacent atoms (e.g., R 2A and R 3A 、R 3A and R 4A 、R 2B and R 3B 、R 3B and R 4B)Together with the atoms to which they are attached (e.g., carbon), and when applicable, independently selected from but not limited to hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxy, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, and a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; The alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; the alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine, and 4',4"-alkyl-substituted triphenylamine; the alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl; other substituted phenyls may include N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, the variable R. 1 , R 2A , R 2B , R 3A , R 3B , R 4A and R 4B Each variable in or two variables on adjacent atoms (e.g., R 2A and R 3A , R 3A and R 4A , R 2B and R 3B , R 3B and R 4B ) together with the atom to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomeric unit, the emitting monomeric unit, or a combination of both the absorbing monomeric unit and the emitting monomeric unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently attached to the main chain, end, or side chain of the polymer. For example, the absorbing monomeric unit and / or the emitting monomeric unit can be attached to the main chain, end, or side chain of the polymer by coupling with R 1 , R 2A , R 2B , R 3A , R 3B , R 4A, R 4B At least one linkage (or linkage via a linker moiety) of R, or any combination thereof, is covalently linked to the polymer. Fig. 6A Examples of monomer units are shown which may be bound to the polymer, for example, by linkage to the R 3A and R 3B groups.
[0358] In some embodiments, the polymer dots of the present disclosure may comprise a polymer comprising absorptive monomer units (e.g., narrowband absorptive monomer units) and / or emissive monomer units having the following formula:
[0359]
[0360] wherein each of R 1 , R 2A , R 2B , R 3A , R 3B , R 4A and R 4B and two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, n = 1-50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted bipyridyl, tripyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted tripyridyl, furyl, alkyl substituted thiophenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted thiophenyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted pyrazolyl, substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted benzoxazolyl, benzo In some embodiments, R is substituted with thiadiazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted benzothiadiazole, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted fluorenyl, triphenylamino-substituted fluorenyl, diphenylamino-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-) substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamino and alkyl-substituted thiophenyl. 1 , R 2A , R 2B , R 3A , R 3B , R 4A and R 4BEach of these or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. As an exemplary embodiment, substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino, and 4',4"-alkyl-substituted triphenylamino; alkyl-substituted thienyls may include 2-alkylthienyl, 3-alkylthienyl, and 4-alkylthienyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. An absorbent monomer unit, an emissive monomer unit, or a combination of both an absorbent monomer unit and an emissive monomer unit may be incorporated into the polymer backbone (e.g., polymerized in the polymer) and / or covalently linked to the polymer backbone, terminus, or side chain. For example, an absorbent monomer unit and / or an emissive monomer unit may be covalently linked to the polymer via at least one linkage (or a linkage via a linker moiety) with R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、or any combination thereof. The monomer unit may be incorporated into the polymer backbone, for example, by attachment to the R 3A and R 3B groups. Figure 6B illustrates examples of monomer units that may be incorporated into the polymer, for example, by attachment to the R 3A and R 3B groups.
[0361] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0362]
[0363] wherein R 1 、R 2A and R 2B each independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or arylalkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino and 4',4"-alkyl-substituted triphenylamino; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 , R 2A and R 2B each of which is independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester and alkynyl. The absorptive monomer unit, emissive monomer unit or a combination of both the absorptive monomer unit and the emissive monomer unit may be incorporated into the polymer backbone (e.g., polymerized in the polymer) and / or covalently linked to the polymer backbone, terminus or side chain. For example, the absorptive monomer unit and / or the emissive monomer unit may be covalently linked to the polymer via, for example, at least one linkage with R 1 , R 2A , R 2B or any combination thereof (or via a linker moiety). Parentheses indicate the point of attachment of the monomer unit to the polymer backbone. Figure 6C Illustrates examples of monomer units that may be combined with the polymer (e.g., copolymerized in the polymer).
[0364] In some embodiments, the polymer dots of the present disclosure may comprise a polymer comprising an absorptive monomer unit (e.g., narrow-band absorptive monomer unit) and / or an emissive monomer unit having the following formula:
[0365]
[0366] wherein R1 , R 2A , R 2B , R 3A and R 3B Each of and R is independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or arylalkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 , R 2A , R 2B , R 3A and R 3B Each of is independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxyl, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomer unit, the emitting monomer unit, or a combination of the absorbing monomer unit and the emitting monomer unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently linked to the main chain, end, or side chain of the polymer. For example, the absorbing monomer unit and / or the emitting monomer unit can be linked to the main chain, end, or side chain of the polymer by combining with R 1 , R 2A , R 2B , R 3A and R 3B or any combination thereof (or a linkage via a linker moiety) is covalently attached to the polymer. Fig.6D Examples of monomer units are shown, which can be obtained by reacting with R 3A and R 3B The groups are connected to the polymer.
[0367] In some embodiments, the polymer dots of the present disclosure may include a polymer including an absorbing monomer unit (eg, a narrow-band absorbing monomer unit) and / or an emissive monomer unit having the following formula:
[0368]
[0369] wherein each of R 1 , R 2A , R 2B , R 3A , R 3B , R 4A , R 4B , R 5A and R 5B , or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; the alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyls, 7-alkyl-9,9-dialkyl-substituted fluorenyls, 6-alkyl-9,9-dialkyl-substituted fluorenyls, 7-triphenylamino-9,9-dialkyl-substituted fluorenyls, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyls; the alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyls, 6-alkyl-substituted carbazolyls, and 7-alkyl-substituted carbazolyls; the alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylaminos, 3'-alkyl-substituted triphenylaminos, 3',4'-dialkyl-substituted triphenylaminos, and 4',4"-alkyl-substituted triphenylaminos; the alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, each of R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、and R 5B or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the backbone of the polymer (e.g., copolymerized in the polymer) and / or covalently linked to the backbone, terminus, or side chain of the polymer. For example, the absorbent monomer unit and / or the emissive monomer unit may be covalently linked to the polymer through at least one linkage (or a linkage via a linker moiety) with R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B or any combination thereof. In certain embodiments, it may be covalently linked to the polymer by linking to R5A and R 5B groups incorporate narrow band monomer units into the backbone. Fig. 6E Examples of monomer units are shown which may be incorporated into the polymer, for example, by attachment to R 5A and R 5B groups.
[0370] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorbent monomer units (e.g., narrow band absorbent monomer units) and / or emissive monomer units having the following formula:
[0371]
[0372] wherein each of R 1A , R 1B , R 2A , R 2B , R 3A and R 3B or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxy, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1A , R 1B , R 2A , R 2B , R 3A and R 3B Each or two variables on adjacent atoms in together with the atom to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomeric unit, the emitting monomeric unit, or a combination of both the absorbing monomeric unit and the emitting monomeric unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently attached to the main chain, end, or side chain of the polymer. For example, the absorbing monomeric unit and / or the emitting monomeric unit can be attached to the main chain, end, or side chain of the polymer by connecting with R 1A , R 1B , R 2A , R 2B , R 3A , R 3B or any combination thereof (or a linkage via a linker moiety) is covalently attached to the polymer. Fig. 6F Examples of monomer units are shown, which can be obtained by reacting with R 1A , R 1B , R 2A , R 2B , R 3A or R3B is bound to the polymer by the linkage of the group.
[0373] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0374]
[0375] wherein R 2A , R 2B , R 3A , R 3B , R 4A , R 4B , R 5A and R 5B each of or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino, and 4',4"-alkyl-substituted triphenylamino; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, each of R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B and two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the polymer backbone (e.g., polymerized in the polymer) and / or covalently linked to the polymer backbone, terminus, or side chain. For example, the absorbent monomer unit and / or the emissive monomer unit may be covalently linked to the polymer through at least one linkage (or a linkage via a linker moiety) with R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B or any combination thereof. Figure 6G shows examples of monomer units that may, for example, be covalently linked to the polymer through a linkage with R 5A and R5B is bound to the polymer by the linkage of the group.
[0376] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0377]
[0378] wherein R 1 , R 2A , R 2B , R 3A , R 3B , R 4A and R 4B each or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, and 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyls, 7-alkyl-9,9-dialkyl-substituted fluorenyls, 6-alkyl-9,9-dialkyl-substituted fluorenyls, 7-triphenylamino-9,9-dialkyl-substituted fluorenyls, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyls; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyls, 6-alkyl-substituted carbazolyls, and 7-alkyl-substituted carbazolyls; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylaminos, 3'-alkyl-substituted triphenylaminos, 3',4'-dialkyl-substituted triphenylaminos, and 4',4"-alkyl-substituted triphenylaminos; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxy-phenyl-4-phenyl, and wherein R. 5A , R 5B , R 6A and R 6B each of which is independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, hydroxy, acyl, cyano, nitro, ethers and their derivatives, esters and their derivatives, alkyl ketones, alkyl esters, aryl esters, alkynyl, alkylamines, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyls, 7-alkyl-9,9-dialkyl-substituted fluorenyls, 6-alkyl-9,9-dialkyl-substituted fluorenyls, 7-triphenylamino-9,9-dialkyl-substituted fluorenyls, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyls; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyls, 6-alkyl-substituted carbazolyls, and 7-alkyl-substituted carbazolyls; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylaminos, 3'-alkyl-substituted triphenylaminos, 3',4'-dialkyl-substituted triphenylaminos, and 4',4"-alkyl-substituted triphenylaminos; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, each of R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B and each of R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R 6A 、R 6B or any combination thereof, and two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the main chain of the polymer (e.g., copolymerized in the polymer) and / or covalently linked to the main chain, end, or side chain of the polymer. For example, the absorbent monomer unit and / or the emissive monomer unit may be covalently linked to the polymer through at least one linkage (or a linkage via a linker moiety) with R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R 6A 、R 6B or any combination thereof. Figure 6Hillustrates examples of monomer units that can be incorporated into a polymer, for example, by attachment to the polymer via a linkage to the R 2A -, R 2B -, R 6A - or R 6B group.
[0379] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0380]
[0381] wherein X represents an aryl and its derivatives, and each of R 1 -, R 2 -, R 3 -, R 4 -, R 5 -, R 6 -, R 7 -, R 8 -, R 9 -, R 10 -, R 11 -, R 12 -, R 13 -, R 14 - and R 15 or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; the alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; the alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; the alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino, and 4',4"-alkyl-substituted triphenylamino; the alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 and each of R 7 R 8 R 9 R 10 R 11 R 12At least one linkage (or linkage via a linker moiety) of or any combination thereof is covalently linked to the backbone, terminus or side chain of the polymer. When X represents anthracene and its derivatives, the absorbent monomer unit, the emissive monomer unit or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the backbone of the polymer, and / or via R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 or any combination thereof, at least one linkage (or linkage via a linker moiety) is covalently linked to the backbone, terminus or side chain of the polymer. The absorbent monomer unit, the emissive monomer unit or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the backbone of the polymer (e.g., polymerized in the polymer) and / or covalently linked to the backbone, terminus or side chain of the polymer. For example, the absorbent monomer unit and / or the emissive monomer unit may be linked to the polymer via R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 or any combination thereof, at least one linkage (or linkage via a linker moiety) is covalently linked to the polymer. Fig.6I illustrates examples of monomer units that may be incorporated into the polymer, for example, via linkage to the R 2 or R 5 group.
[0382] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes an absorbent monomer unit (e.g., a narrow-band absorbent monomer unit) and / or an emissive monomer unit having the following formula:
[0383]
[0384] wherein X represents aryl and its derivatives, R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R4B , R 5A , R 5B , R 6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A , R 9B , R 10A , R 10B , R 11A , R 11B , R 12A and R 12B Each of or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxy, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino, and 4',4"-alkyl-substituted triphenylamino; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R 6A 、R 6B 、R 7A 、R 7B 、R 8A 、R 8B 、R 9A 、R 9B 、R 10A 、R 10B 、R 11A 、R 11B 、R 12A and R 12BEach of these or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), when applicable, is independently selected from but not limited to hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit can be incorporated into the backbone of the polymer (e.g., polymerized in the polymer) and / or covalently linked to the backbone, ends, or side chains of the polymer. For example, the absorbent monomer unit and / or the emissive monomer unit can be covalently linked to the polymer through at least one linkage (or linkage via a linker moiety) with R 1 、R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R 6A 、R 6B 、R 7A 、R 7B 、R 8A 、R 8B 、R 9A 、R 9B 、R 10A 、R 10B 、R 11A 、R 11B 、R 12A 、R 12B or any combination thereof. Figure 6J shows examples of monomer units that can be incorporated into the polymer, for example, by linkage with the R 4A or R 4B groups.
[0385] In some embodiments, the polymer dots of the present disclosure can include a polymer comprising an absorbent monomer unit (e.g., a narrow-band absorbent monomer unit) and / or an emissive monomer unit having the following formula:
[0386]
[0387] where R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A and R 9B Each of or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, is independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or arylalkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 2A , R 2B , R 3A , R 3B , R 4A , R 4B , R 5A , R 5B , R 6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A and R 9B Each or two variables on adjacent atoms in together with the atom to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomeric unit, the emitting monomeric unit, or a combination of both the absorbing monomeric unit and the emitting monomeric unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently attached to the main chain, end, or side chain of the polymer. For example, the absorbing monomeric unit and / or the emitting monomeric unit can be attached to the main chain, end, or side chain of the polymer by connecting with R 2A , R 2B , R 3A , R 3B , R 4A , R 4B, R 5A , R 5B , R 6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A , R 9B or at least one linkage (or linkage via a linker moiety) of any combination thereof is covalently linked to the polymer. Figure 6K illustrates examples of monomer units that can be combined with a polymer, for example, by linkage to an R 4A or R 4B group.
[0388] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrowband absorptive monomer units) and / or emissive monomer units having the following formula:
[0389]
[0390] wherein each of R 2A , R 2B , R 3A , R 3B , R 4A , R 4B , R 5A , R 5B , R 6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A , R 9B , R 10 , R 11 , R 12 and R 13 and two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, independently selected, when applicable, from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyls, 7-alkyl-9,9-dialkyl-substituted fluorenyls, 6-alkyl-9,9-dialkyl-substituted fluorenyls, 7-triphenylamino-9,9-dialkyl-substituted fluorenyls, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyls; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyls, 6-alkyl-substituted carbazolyls, and 7-alkyl-substituted carbazolyls; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylaminos, 3'-alkyl-substituted triphenylaminos, 3',4'-dialkyl-substituted triphenylaminos, and 4',4"-alkyl-substituted triphenylaminos; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, R 2A 、R 2B 、R 3A 、R 3B 、R 4A 、R 4B 、R 5A 、R 5B 、R 6A 、R 6B 、R 7A 、R 7B 、R 8A 、R 8B 、R 9A 、R 9B 、R 10 、R 11 、R 12 and each of R 13 or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the polymer backbone (e.g., polymerized in the polymer) and / or covalently linked to the polymer backbone, ends, or side chains. For example, the absorbent monomer unit and / or the emissive monomer unit may be attached to R 2A 、R 2B, R 3A , R 3B , R 4A , R 4B , R 5A , R 5B , R 6A , R 6B , R 7A , R 7B , R 8A , R 8B , R 9A , R 9B , R 10 , R 11 , R 12 , R 13 or at least one linkage (or linkage via a linker moiety) of any combination thereof is covalently linked to the polymer. Figure 6L illustrates examples of monomer units that can be bound to the polymer, for example, by linkage to an R 4A or an R 4B group.
[0391] In some embodiments, the polymer dots of the present disclosure can comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0392]
[0393] where each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Each or two variables on adjacent atoms in together with the atom to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomeric unit, the emitting monomeric unit, or a combination of both the absorbing monomeric unit and the emitting monomeric unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently attached to the main chain, end, or side chain of the polymer. For example, the absorbing monomeric unit and / or the emitting monomeric unit can be attached to the main chain, end, or side chain of the polymer by connecting with R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or any combination thereof (or a linkage via a linker moiety) is covalently attached to the polymer. Figure 6M Examples of monomer units are shown, which can be obtained by reacting with R 2 The polymer is bound to the molecule by attachment (e.g., via a linker moiety).
[0394] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorptive monomer units (e.g., narrow-band absorptive monomer units) and / or emissive monomer units having the following formula:
[0395]
[0396] wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyls, 7-alkyl-9,9-dialkyl-substituted fluorenyls, 6-alkyl-9,9-dialkyl-substituted fluorenyls, 7-triphenylamino-9,9-dialkyl-substituted fluorenyls, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyls; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyls, 6-alkyl-substituted carbazolyls, and 7-alkyl-substituted carbazolyls; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylaminos, 3'-alkyl-substituted triphenylaminos, 3',4'-dialkyl-substituted triphenylaminos, and 4',4"-alkyl-substituted triphenylaminos; alkyl-substituted thio-phenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 each, or two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the backbone of the polymer (e.g., polymerized in the polymer) and / or covalently linked to the backbone, terminus, or side chain of the polymer. For example, the absorbent monomer unit and / or the emissive monomer unit may be attached to R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10At least one linkage (or linkage via a linker moiety) of or any combination thereof is covalently linked to the polymer. Figure 6M Examples of monomer units are shown which can be bound to the polymer, for example, by linkage to R 1 (e.g., via a linker moiety).
[0397] In some embodiments, the polymer dots of the present disclosure can include a polymer that includes absorptive monomer units (e.g., narrowband absorptive monomer units) and / or emissive monomer units having the following formula:
[0398]
[0399] wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, substituents may include alkyl-aryl-substituted carbazoles (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); alkyl-substituted phenyls may include 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 3,5-dialkylphenyl, 3,4-dialkylphenyl; alkyl-substituted fluorenyls may include 9,9-dialkyl-substituted fluorenyl, 7-alkyl-9,9-dialkyl-substituted fluorenyl, 6-alkyl-9,9-dialkyl-substituted fluorenyl, 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and 7-diphenylamino-9,9-dialkyl-substituted fluorenyl; alkyl-substituted carbazolyls may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl, and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylaminos may include 4'-alkyl-substituted triphenylamino, 3'-alkyl-substituted triphenylamino, 3',4'-dialkyl-substituted triphenylamino, and 4',4"-alkyl-substituted triphenylamino; alkyl-substituted thiophenyls may include 2-alkylthiophenyl, 3-alkylthiophenyl, and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl, and N-dialkoxyphenyl-4-phenyl. In some embodiments, each of R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and two variables on adjacent atoms together with the atoms (e.g., carbon) to which they are attached, where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl), heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbent monomer unit, the emissive monomer unit, or a combination of both the absorbent monomer unit and the emissive monomer unit may be incorporated into the polymer backbone (e.g., polymerized in the polymer) and / or covalently linked to the polymer backbone, termini, or side chains. For example, the absorbent monomer unit and / or the emissive monomer unit may be covalently linked to the polymer through at least one linkage (or a linkage via a linker moiety) with R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 or any combination thereof. Figure 6MExamples of monomer units are shown, which can be combined with a polymer, for example, by connection with R 5 (e.g., via a linker moiety).
[0400] In some embodiments, the polymer dots of the present disclosure may comprise a polymer that includes absorbent monomer units (e.g., narrow-band absorbent monomer units) and / or emissive monomer units having the following formula:
[0401]
[0402] where each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 or two variables on adjacent atoms together with the atoms to which they are attached (e.g., carbon), where applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight-chain or branched alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ether and its derivatives, ester and its derivatives, alkyl ketone, alkyl ester, aryl ester, alkynyl, alkylamine, fluoroalkyl, fluoroaryl, and polyalkylene (e.g., methoxyethoxyethoxy, ethoxyethoxy, and -(OCH2CH2) nOH, where n = 1 - 50), phenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted phenyl, pyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyridyl, bipyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted bipyridyl, terpyridyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted terpyridyl, furyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted furyl, thienyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thienyl, pyrrolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrrolyl, pyrazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazolyl, oxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted oxazolyl, thiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted thiazolyl, imidazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted imidazolyl, pyrazinyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted pyrazinyl, benzoxazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzoxazolyl, benzothiadiazolyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted benzothiadiazolyl, fluorenyl, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted fluorenyl, triphenylamine-substituted fluorenyl, diphenylamine-substituted fluorenyl, carbazole, alkyl-(alkoxy-, aryl-, fluoroalkyl-, fluoroaryl-)substituted carbazole, carbazolyl, alkyl-substituted carbazolyl, alkyl-substituted triphenylamine and alkyl-substituted thiophenyl.As an exemplary embodiment, the substituent may include an alkyl-aryl-substituted carbazole (e.g., 3,6-di-tert-butyl-9-phenyl-9H-carbazole); the alkyl-substituted phenyl may include a 2-alkylphenyl, a 3-alkylphenyl, a 4-alkylphenyl, a 2,4-dialkylphenyl, a 3,5-dialkylphenyl, a 3,4-dialkylphenyl; the alkyl-substituted fluorenyl may include a 9,9-dialkyl-substituted fluorenyl, a 7-alkyl-9,9-dialkyl-substituted fluorenyl, a 6-alkyl-9,9-dialkyl-substituted fluorenyl, a 7-triphenylamino-9,9-dialkyl-substituted fluorenyl, and a 7-diphenylamino-9,9-dialkyl-substituted fluorenyl. substituted fluorenyl; alkyl-substituted carbazolyl may include N-alkyl-substituted carbazolyl, 6-alkyl-substituted carbazolyl and 7-alkyl-substituted carbazolyl; alkyl-substituted triphenylamine may include 4'-alkyl-substituted triphenylamine, 3'-alkyl-substituted triphenylamine, 3',4'-dialkyl-substituted triphenylamine and 4',4"-alkyl-substituted triphenylamine; alkyl-substituted thiophenyl may include 2-alkylthiophenyl, 3-alkylthiophenyl and 4-alkylthiophenyl, N-dialkyl-4-phenyl, N-diphenyl-4-phenyl and N-dialkoxyphenyl-4-phenyl. In some embodiments, R. 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each or two variables on adjacent atoms in together with the atom to which they are attached (e.g., carbon), when applicable, are independently selected from, but not limited to, hydrogen (H), deuterium (D), halogen, straight or branched chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, cycloalkylene, heterocycloalkylene, cycloalkenyl, heterocycloalkenyl, alkoxy, aryl, alkaryl (or aralkyl) heteroaryl, aryloxy, hydroxy, acyl, cyano, nitro, azide, carboxyl, amino, sulfide, ester, and alkynyl. The absorbing monomeric unit, the emitting monomeric unit, or a combination of both the absorbing monomeric unit and the emitting monomeric unit can be incorporated into the main chain of the polymer (e.g., polymerized in the polymer) and / or covalently attached to the main chain, end, or side chain of the polymer. For example, the absorbing monomeric unit and / or t...
Claims
1. A nanoparticle comprising a polymer, the polymer comprising: An absorbent monomer unit, the absorbent monomer unit comprising BODIPY, a BODIPY derivative, diBODIPY, a diBODIPY derivative, an Atto dye, rhodamine, a rhodamine derivative, coumarin, a coumarin derivative, cyanine, a cyanine derivative, pyrene, a pyrene derivative, squaric acid, a squaric acid derivative, or any combination thereof; and An emissive monomer unit; Wherein the absorption width of the nanoparticles at 10% of the absorbance maximum is less than 150 nm; Wherein the number ratio of the absorbent monomer unit to the emissive monomer unit is greater than 4:
1.
2. The nanoparticle according to claim 1, wherein the polymer further comprises one or more monomer units different from the absorbent monomer unit and the emissive monomer unit.
3. The nanoparticle according to claim 2, wherein the polymer comprises 2 monomer units different from the absorbent monomer unit and the emissive monomer unit.
4. The nanoparticle according to claim 2, wherein the one or more monomer units different from the absorbent monomer unit and the emissive monomer unit comprise general monomer units, functional monomer units, energy transfer monomer units, second absorbent monomer units, or any combination thereof.
5. The nanoparticle according to claim 4, wherein the functional monomer unit comprises a hydrophilic monomer unit.
6. The nanoparticle according to any one of claims 1 to 5, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and an energy transfer unit.
7. The nanoparticle according to any one of claims 1 to 5, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, an energy transfer unit, and a functional monomer unit.
8. The nanoparticle according to any one of claims 1 to 5, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and a functional monomer unit.
9. The nanoparticle according to any one of claims 1 to 5, wherein the polymer further comprises an additional second absorbent monomer unit.
10. The nanoparticle according to any one of claims 1 to 5, wherein the nanoparticle comprises an absorption peak having a wavelength longer than 450 nm.
11. The nanoparticle according to any one of claims 1 to 5, wherein the nanoparticle has an absorption spectrum with a FWHM of 80 nm or less.
12. The nanoparticle according to any one of claims 1 to 5, wherein the polymer comprises: The main chain comprising the absorbent monomer unit, the side chain comprising the absorbent monomer unit, the end comprising the absorbent monomer unit, or any combination thereof.
13. The nanoparticle according to any one of claims 1 to 5, wherein the absorbent monomer unit comprises BODIPY, BODIPY derivatives, or any combination thereof.
14. The nanoparticle according to any one of claims 1 to 5, further comprising a matrix polymer.
15. The nanoparticle according to claim 14, wherein the matrix polymer is a non-semiconductor polymer.
16. The nanoparticle according to claim 14, wherein the matrix polymer is a semiconductor polymer.
17. The nanoparticle according to any one of claims 1 to 5, wherein the diameter of the nanoparticle is less than 1000 nm, and the diameter is measured by dynamic light scattering.
18. The nanoparticle according to any one of claims 1 to 5, wherein the quantum yield of the nanoparticle is greater than 5%.
19. The nanoparticle according to any one of claims 1 to 5, wherein the absorbent monomer unit is 30% or less of the total mass of the nanoparticle.
20. The nanoparticle according to any one of claims 1 to 5, wherein the absorbent monomer unit is 30% or more of the total mass of the nanoparticle.
21. The nanoparticle according to any one of claims 1 to 5, wherein the polymer further comprises a blend of polymers.
22. The nanoparticle according to any one of claims 1 to 5, wherein the number ratio of the emissive monomer unit to the absorbent monomer unit is less than 1:
2.
23. The nanoparticle according to any one of claims 1 to 5, wherein the brightness of the nanoparticle is greater than 1.0×10 -13 cm 2 , and the brightness is calculated as the product of the quantum yield and the absorption cross-section.
24. The nanoparticle according to any one of claims 1 to 5, wherein the nanoparticle is bioconjugated to a biomolecule.
25. The nanoparticle according to claim 24, wherein the biomolecule comprises a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof.
26. The nanoparticle according to claim 24, wherein the biomolecule comprises an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof.
27. The nanoparticle according to any one of claims 1 to 5, wherein the nanoparticle does not comprise a β-phase structure.
28. The nanoparticle according to any one of claims 1 to 5, wherein the nanoparticle does not comprise a fluorene monomer unit.
29. A nanoparticle comprising a polymer, the polymer comprising: An absorbent monomer unit, the absorbent monomer unit comprising BODIPY, a BODIPY derivative, diBODIPY, a diBODIPY derivative, an Atto dye, rhodamine, a rhodamine derivative, coumarin, a coumarin derivative, cyanine, a cyanine derivative, pyrene, a pyrene derivative, squaric acid, a squaric acid derivative, or any combination thereof; and An emissive monomer unit; Wherein the number ratio of the absorbent monomer unit to the emissive monomer unit is greater than 4:
1.
30. The nanoparticle according to claim 29, wherein the polymer further comprises one or more monomer units different from the absorbent monomer unit and the emissive monomer unit.
31. The nanoparticle according to claim 30, wherein the polymer comprises 2 monomer units different from the absorbent monomer unit and the emissive monomer unit.
32. The nanoparticle according to claim 30, wherein the one or more monomer units different from the absorbent monomer unit and the emissive monomer unit comprise general monomer units, functional monomer units, energy transfer monomer units, second absorbent monomer units, or any combination thereof.
33. The nanoparticle according to claim 32, wherein the functional monomer unit comprises a hydrophilic monomer unit.
34. The nanoparticle according to any one of claims 29 to 33, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and an energy transfer unit.
35. The nanoparticle according to any one of claims 29 to 33, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, an energy transfer unit, and a functional monomer unit.
36. The nanoparticle according to any one of claims 29 to 33, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and a functional monomer unit.
37. The nanoparticle according to any one of claims 29 to 33, wherein the polymer further comprises an additional second absorbent monomer unit.
38. The nanoparticle according to any one of claims 29 to 33, wherein the nanoparticle comprises an absorption peak having a wavelength longer than 450 nm.
39. The nanoparticle according to any one of claims 29 to 33, wherein the nanoparticle has an absorption spectrum with an FWHM of 80 nm or less.
40. The nanoparticle according to any one of claims 29 to 33, wherein the polymer comprises: The main chain comprising the absorbent monomer unit, the side chain comprising the absorbent monomer unit, the end comprising the absorbent monomer unit, or any combination thereof.
41. The nanoparticle according to any one of claims 29 to 33, wherein the absorbent monomer unit comprises BODIPY, a BODIPY derivative, or any combination thereof.
42. The nanoparticle according to any one of claims 29 to 33, further comprising a matrix polymer.
43. The nanoparticle according to claim 42, wherein the matrix polymer is a non-semiconductor polymer.
44. The nanoparticle according to claim 42, wherein the matrix polymer is a semiconductor polymer.
45. The nanoparticle according to any one of claims 29 to 33, wherein the diameter of the nanoparticle is less than 1000 nm, and the diameter is measured by dynamic light scattering.
46. The nanoparticle according to any one of claims 29 to 33, wherein the quantum yield of the nanoparticle is greater than 5%.
47. The nanoparticle according to any one of claims 29 to 33, wherein the absorbent monomer unit is 30% or less of the total mass of the nanoparticle.
48. The nanoparticle according to any one of claims 29 to 33, wherein the absorbent monomer unit is 30% or more of the total mass of the nanoparticle.
49. The nanoparticle according to any one of claims 29 to 33, wherein the polymer further comprises a blend of polymers.
50. The nanoparticle according to any one of claims 29 to 33, wherein the number ratio of the emissive monomer unit to the absorbent monomer unit is less than 1:
2.
51. The nanoparticle according to any one of claims 29 to 33, wherein the absorption width of the nanoparticle at 10% of the absorbance maximum is less than 150 nm.
52. The nanoparticle according to any one of claims 29 to 33, wherein the absorption width of the nanoparticle at 10% of the absorbance maximum is from 10 nm to 150 nm.
53. The nanoparticle according to any one of claims 29 to 33, wherein the brightness of the nanoparticle is greater than 1.0×10 -13 cm 2 , and the brightness is calculated as the product of the quantum yield and the absorption cross section.
54. The nanoparticle according to any one of claims 29 to 33, wherein the nanoparticle is bioconjugated to a biomolecule.
55. The nanoparticle according to claim 54, wherein the biomolecule comprises a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof.
56. The nanoparticle according to claim 54, wherein the biomolecule comprises an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof.
57. The nanoparticle according to any one of claims 29 to 33, wherein the nanoparticle does not include a β-phase structure.
58. The nanoparticle according to any one of claims 29 to 33, wherein the nanoparticle does not include a fluorene monomer unit.
59. A nanoparticle comprising a polymer, the polymer comprising: A first absorbent monomer unit, the absorbent monomer unit comprising BODIPY, a BODIPY derivative, diBODIPY, a diBODIPY derivative, an Atto dye, rhodamine, a rhodamine derivative, coumarin, a coumarin derivative, cyanine, a cyanine derivative, pyrene, a pyrene derivative, squaric acid, a squaric acid derivative, or any combination thereof; An emissive monomer unit; And One or more monomer units different from the absorbent monomer unit and the emissive monomer unit; Wherein the absorption width of the nanoparticles at 15% of the absorbance maximum is less than 150 nm; Wherein the number ratio of the absorbent monomer unit to the emissive monomer unit is greater than 4:
1.
60. The nanoparticle according to claim 59, wherein the polymer comprises two monomer units different from the absorbent monomer unit and the emissive monomer unit.
61. The nanoparticle according to claim 59, wherein the one or more monomer units different from the absorbent monomer unit and the emissive monomer unit comprise a general monomer unit, a functional monomer unit, an energy transfer monomer unit, a second absorbent monomer unit, or any combination thereof.
62. The nanoparticle according to claim 61, wherein the functional monomer unit comprises a hydrophilic monomer unit.
63. The nanoparticle according to any one of claims 59 to 62, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and an energy transfer unit.
64. The nanoparticle according to any one of claims 59 to 62, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, an energy transfer unit, and a functional monomer unit.
65. The nanoparticle according to any one of claims 59 to 62, wherein the polymer comprises a first absorbent monomer unit, an emissive monomer unit, and a functional monomer unit.
66. The nanoparticle according to any one of claims 59 to 62, wherein the polymer further comprises an additional second absorbent monomer unit.
67. The nanoparticle according to any one of claims 59 to 62, wherein the nanoparticle comprises an absorption peak having a wavelength longer than 450 nm.
68. The nanoparticle according to any one of claims 59 to 62, wherein the nanoparticle has an absorption spectrum with an FWHM of 80 nm or less.
69. The nanoparticle according to any one of claims 59 to 62, wherein the polymer comprises: The main chain comprising the absorbent monomer unit, the side chain comprising the absorbent monomer unit, the end comprising the absorbent monomer unit, or any combination thereof.
70. The nanoparticles according to any one of claims 59 to 62, wherein the absorbent monomer unit comprises BODIPY, a BODIPY derivative, or any combination thereof.
71. The nanoparticles according to any one of claims 59 to 62, further comprising a matrix polymer.
72. The nanoparticles according to claim 71, wherein the matrix polymer is a non-semiconductor polymer.
73. The nanoparticles according to claim 71, wherein the matrix polymer is a semiconductor polymer.
74. The nanoparticles according to any one of claims 59 to 62, wherein the diameter of the nanoparticles is less than 1000 nm, which is measured by dynamic light scattering.
75. The nanoparticles according to any one of claims 59 to 62, wherein the quantum yield of the nanoparticles is greater than 5%.
76. The nanoparticles according to any one of claims 59 to 62, wherein the absorbent monomer unit is 30% or less of the total mass of the nanoparticles.
77. The nanoparticles according to any one of claims 59 to 62, wherein the absorbent monomer unit is 30% or more of the total mass of the nanoparticles.
78. The nanoparticles according to any one of claims 59 to 62, wherein the polymer further comprises a blend of polymers.
79. The nanoparticles according to any one of claims 59 to 62, wherein the number ratio of the emissive monomer unit to the absorbent monomer unit is less than 1:
2.
80. The nanoparticles according to any one of claims 59 to 62, wherein the absorption width of the nanoparticles at 10% of the absorbance maximum is less than 150 nm.
81. The nanoparticles according to any one of claims 59 to 62, wherein the absorption width of the nanoparticles at 10% of the absorbance maximum is from 10 nm to 150 nm.
82. The nanoparticles according to any one of claims 59 to 62, wherein the brightness of the nanoparticles is greater than 1.0×10 -13 cm 2 , and the brightness is calculated as the product of the quantum yield and the absorption cross-section.
83. The nanoparticles according to any one of claims 59 to 62, wherein the nanoparticles are bioconjugated to a biomolecule.
84. The nanoparticles according to claim 83, wherein the biomolecule comprises a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof.
85. The nanoparticle according to claim 83, wherein the biomolecule comprises an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof.
86. The nanoparticle according to any one of claims 59 to 62, wherein the nanoparticle does not comprise a β-phase structure.
87. The nanoparticle according to any one of claims 59 to 62, wherein the nanoparticle does not comprise a fluorene monomer unit.
88. A nanoparticle, comprising: A first polymer, the first polymer comprising an absorbent monomer unit, the absorbent monomer unit comprising BODIPY, a BODIPY derivative, diBODIPY, a diBODIPY derivative, an Atto dye, rhodamine, a rhodamine derivative, coumarin, a coumarin derivative, cyanine, a cyanine derivative, pyrene, a pyrene derivative, squaric acid, a squaric acid derivative, or any combination thereof; and A second polymer, the second polymer comprising an emissive monomer unit, Wherein the absorption width of the nanoparticles at 15% of the absorbance maximum is less than 150 nm; Wherein the number ratio of the absorbent monomer unit to the emissive monomer unit is greater than 4:
1.
89. The nanoparticle according to claim 88, wherein the absorbent monomer unit comprises BODIPY, a BODIPY derivative, or any combination thereof.
90. The nanoparticle according to claim 88, wherein the first polymer and the second polymer are the same polymer.
91. The nanoparticle according to any one of claims 88 to 90, wherein the first polymer has a main chain comprising the absorbent monomer unit, a side chain comprising the absorbent monomer unit, an end comprising the absorbent monomer unit, or any combination thereof.
92. The nanoparticle according to any one of claims 88 to 90, wherein the first polymer is a semiconductor polymer, the second polymer is a semiconductor polymer, or both the first polymer and the second polymer are semiconductor polymers.
93. The nanoparticle according to any one of claims 88 to 90, wherein the mass ratio of the first polymer to the second polymer is greater than 1:
1.
94. The nanoparticle according to any one of claims 88 to 90, further comprising a matrix polymer.
95. The nanoparticle according to claim 94, wherein the matrix polymer is a non-semiconductor polymer.
96. The nanoparticle according to claim 94, wherein the matrix polymer is a semiconductor polymer.
97. The nanoparticle according to any one of claims 88 to 90, wherein the diameter of the nanoparticle is less than 1000 nm, which is measured by dynamic light scattering.
98. The nanoparticle according to any one of claims 88 to 90, wherein the quantum yield of the nanoparticle is greater than 5%.
99. The nanoparticle according to any one of claims 88 to 90, wherein the absorbent monomer unit is 30% or less of the total mass of the nanoparticle.
100. The nanoparticle according to any one of claims 88 to 90, wherein the absorbent monomer unit is 30% or more of the total mass of the nanoparticle.
101. The nanoparticle according to any one of claims 88 to 90, wherein the polymer further comprises a blend of polymers.
102. The nanoparticle according to any one of claims 88 to 90, wherein the ratio of the number of emissive monomer units to the number of absorbent monomer units is less than 1:
2.
103. The nanoparticle according to any one of claims 88 to 90, wherein the absorption width of the nanoparticle at 10% of the absorbance maximum is less than 150 nm.
104. The nanoparticle according to any one of claims 88 to 90, wherein the absorption width of the nanoparticle at 10% of the absorbance maximum is from 10 nm to 150 nm.
105. The nanoparticle according to any one of claims 88 to 90, wherein the brightness of the nanoparticle is greater than 1.0×10 -13 cm 2 , and the brightness is calculated as the product of the quantum yield and the absorption cross-section.
106. The nanoparticle according to any one of claims 88 to 90, wherein the nanoparticle is bioconjugated to a biomolecule.
107. The nanoparticle according to claim 106, wherein the biomolecule comprises a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof.
108. The nanoparticle according to claim 106, wherein the biomolecule comprises an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof.
109. The nanoparticle according to any one of claims 88 to 90, wherein the nanoparticle does not comprise a β-phase structure.
110. The nanoparticle according to any one of claims 88 to 90, wherein the nanoparticle does not comprise a fluorene monomer unit.
111. A nanoparticle, comprising: A first polymer, the first polymer comprising absorbent monomer units, the absorbent monomer units comprising BODIPY, BODIPY derivatives, diBODIPY, diBODIPY derivatives, Atto dyes, rhodamines, rhodamine derivatives, coumarins, coumarin derivatives, cyanines, cyanine derivatives, pyrenes, pyrene derivatives, squaric acids, squaric acid derivatives, or any combination thereof; and A second polymer, the second polymer comprising emissive monomer units; wherein the number ratio of absorbent monomer units to emissive monomer units is greater than 4:
1.
112. The nanoparticle according to claim 111, wherein the absorption width of the nanoparticle at 10% of the maximum absorbance is less than 150 nm.
113. The nanoparticle according to any one of claims 111 to 112, wherein the first polymer and the second polymer are the same polymer.
114. The nanoparticle according to any one of claims 111 to 112, wherein the first polymer has a main chain including the absorbent monomer unit, has a side chain including the absorbent monomer unit, has an end including the absorbent monomer unit, or any combination thereof.
115. The nanoparticle according to any one of claims 111 to 112, wherein the first polymer is a semiconductor polymer, the second polymer is a semiconductor polymer, or both the first polymer and the second polymer are semiconductor polymers.
116. The nanoparticle according to any one of claims 111 to 112, wherein the mass ratio of the first polymer to the second polymer is greater than 1:
1.
117. The nanoparticle according to any one of claims 111 to 112, further comprising a matrix polymer.
118. The nanoparticle according to claim 117, wherein the matrix polymer is a non-semiconductor polymer.
119. The nanoparticle according to claim 117, wherein the matrix polymer is a semiconductor polymer.
120. The nanoparticle according to any one of claims 111 to 112, wherein the diameter of the nanoparticle is less than 1000 nm, and the diameter is measured by dynamic light scattering.
121. The nanoparticle according to any one of claims 111 to 112, wherein the quantum yield of the nanoparticle is greater than 5%.
122. The nanoparticle according to any one of claims 111 to 112, wherein the absorbent monomer unit is 30% or less of the total mass of the nanoparticle.
123. The nanoparticle according to any one of claims 111 to 112, wherein the absorbent monomer unit is 30% or more of the total mass of the nanoparticle.
124. The nanoparticle according to any one of claims 111 to 112, wherein the polymer further comprises a blend of polymers.
125. The nanoparticle according to any one of claims 111 to 112, wherein the number ratio of the emissive monomer unit to the absorbent monomer unit is less than 1:
2.
126. The nanoparticle according to any one of claims 111 to 112, wherein the absorption width of the nanoparticle at 10% of the maximum absorbance is less than 150 nm.
127. The nanoparticle according to any one of claims 111 to 112, wherein the absorption width of the nanoparticle at 10% of the maximum absorbance is from 10 nm to 150 nm.
128. The nanoparticle according to any one of claims 111 to 112, wherein the brightness of the nanoparticle is greater than 1.0×10 -13 cm 2 , and the brightness is calculated as the product of the quantum yield and the absorption cross-section.
129. The nanoparticle according to any one of claims 111 to 112, wherein the nanoparticle is bioconjugated to a biomolecule.
130. The nanoparticle according to claim 129, wherein the biomolecule comprises a protein, a nucleic acid molecule, a lipid, a peptide, a carbohydrate, or any combination thereof.
131. The nanoparticle according to claim 129, wherein the biomolecule comprises an aptamer, a drug, an antibody, an enzyme, a nucleic acid, or any combination thereof.
132. The nanoparticle according to any one of claims 111 to 112, wherein the nanoparticle does not comprise a β-phase structure.
133. The nanoparticle according to any one of claims 111 to 112, wherein the nanoparticle does not comprise a fluorene monomer unit.
134. A method for preparing the nanoparticle according to any one of claims 1 to 133, the method comprising: Providing a solution comprising a polymer, the polymer comprising: Absorbent monomer units; and Emissive monomer units; and Collapsing the polymer to form the nanoparticles.
135. The method according to claim 134, wherein the absorbent monomer unit comprises BODIPY, a BODIPY derivative, or any combination thereof.
136. The method according to claim 134 or 135, wherein the polymer has a main chain comprising the absorbent monomer unit, a side chain comprising the absorbent monomer unit, an end comprising the absorbent monomer unit, or any combination thereof.
137. The method according to claim 134 or 135, wherein the collapsing step comprises combining the solution with an aqueous liquid.
138. The method according to claim 134 or 135, wherein the nanoparticles are formed by nanoprecipitation.
139. A method for preparing nanoparticles according to any one of claims 88 to 133, the method comprising: Providing a solution, the solution comprising: A first polymer, the first polymer comprising absorbent monomer units; and A second polymer, the second polymer comprising emissive monomer units; and Collapsing the first polymer and the second polymer to form the nanoparticles.
140. The method according to claim 139, wherein the absorbent monomer unit comprises BODIPY, a BODIPY derivative, or any combination thereof.
141. The method according to claim 139 or 140, wherein the first polymer has a main chain comprising the absorbent monomer unit, a side chain comprising the absorbent monomer unit, an end comprising the absorbent monomer unit, or any combination thereof.
142. The method according to claim 139 or 140, wherein the collapsing step comprises combining the solution with an aqueous liquid.
143. The method according to claim 139 or 140, wherein the nanoparticles are formed by nanoprecipitation.
144. A method for analyzing a biomolecule, the method comprising optically detecting the presence or absence of the biomolecule with a detector, wherein the biomolecule is linked to nanoparticles according to any one of claims 1 to 133.
145. The method according to claim 144, further comprising imaging the biomolecule, wherein the detector comprises an imaging device.
146. The method according to claim 145, wherein the detector is selected from a camera, an electron multiplier, a charge-coupled device (CCD) image sensor, a photomultiplier tube (PMT), an avalanche photodiode (APD), a single-photon avalanche diode (SPAD), and a complementary metal-oxide semiconductor (CMOS) image sensor.
147. The method according to claim 145, wherein the detector comprises a light detector, an electrical detector, an acoustic detector, a magnetic detector, or the detector incorporates fluorescence microscopy imaging.
148. The method according to any one of claims 144 to 147, further comprising performing an assay.
149. The method according to claim 148, wherein the assay comprises a digital assay.
150. The method according to claim 148 or 149, wherein the assay comprises fluorescence-activated sorting.
151. The method according to claim 148 or 149, wherein the determination comprises flow cytometry.
152. The method according to claim 148 or 149, wherein the determination comprises RNA extraction, cDNA synthesis, gene microarray, DNA extraction, polymerase chain reaction (PCR), isothermal nucleic acid amplification, strand displacement amplification (SDA), DNA methylation analysis, cell culture, comparative genomic hybridization (CGH) study, electrophoresis, Southern blot analysis, enzyme-linked immunosorbent assay (ELISA), digital nucleic acid determination, digital protein determination, or any combination thereof.
153. The method according to claim 148 or 149, wherein the determination comprises a determination for determining the content of microRNA and siRNA, a determination for determining the DNA / RNA content, a determination for determining the lipid content, a determination for determining the protein content, a determination for determining the carbohydrate content, a functional cell determination, or any combination thereof.
154. The method according to any one of claims 144 to 147, further comprising amplifying the biomolecule to produce an amplification product, the amplification comprising performing polymerase chain reaction (PCR), isothermal nucleic acid amplification, rolling circle amplification (RCA), nucleic acid sequence-based amplification (NASBA), loop-mediated amplification (LAMP), strand displacement amplification (SDA), or any combination thereof.
155. The method according to any one of claims 144 to 147, wherein: Analyzing a plurality of biomolecules; and Attaching at least a portion of the plurality of biomolecules to the nanoparticles according to any one of claims 1 to 133.
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