Use of Particles for Optical Filtering

Abstract

1. A composition for light filtering, the composition comprising: a base material comprising a HEMA-based material; a plurality of metallic nanoparticles dispersed in the base material, the plurality of metallic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of metallic nanoparticles.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 17 / 661,112, filed April 28, 2022, which is incorporated by reference in its entirety.

[0002] FIELD OF THEINVENTION This application relates generally to optical filters and, more particularly, to nanoparticles configured for filtering light. [Background technology]

[0003] A method is described in US 2007 / 0298242 A1 that describes the dispersion of metal nanoparticles for optical filtering in sunglasses. Gold nanoparticles or dyes are dispersed in a polymer matrix, and the composite either acts as a lens itself or is used as a coating on one or both sides of a lens. US 2007 / 0298242 A1 does not disclose information regarding the immobilization of light filtering materials in a polymer matrix, which is necessary for the integration of light filtering materials into soft materials.

[0004] Another example of incorporating nanoparticles into a polymer matrix is ​​described in US Patent Application Publication No. 20080203592(A1), in which dry hydrogel contact lenses are hydrated in a hydration solution, the hydration solution containing silver ions, silver nanoparticles, or a combination thereof, a lubricant or wetting agent, or a combination thereof. The silver nanoparticles and / or the lubricant or wetting agent are adsorbed onto and / or encapsulated in the hydrogel contact lens during the extraction and / or hydration steps. The described method may be convertible to gold nanoparticles and / or dyes, but the patent does not disclose information regarding the chemical embedding of these materials into the light filtering material or the final product. The nanoparticles are added after the contact lens is cured, which has an effect on the nanoparticle distribution within the contact lens.

[0005] A method for blocking light in the green region is described in US Patent No. 10054803 (B2). This patent aims to improve color discrimination by using multilayer optical films with strong and narrow reflection bands in the green region. This reference provides reflection as the mechanism for light filtering, the use of chemical dyes as light filtering materials, and the use of multilayer optical films.

[0006] A method for providing contact lenses that selectively block green light is described in a paper by Badawy et al., 2018. The study involves incubating contact lenses in a solution of Rhodamine B dye dissolved in water to produce colored contact lenses for treating color vision deficiencies. Blocking green light (specifically 545-575 nm) has been shown to improve color perception in a simulated color vision deficiency model. As with U.S. Patent Application Publication No. 20080203592(A1), incorporation of the light blocking material relies on passive diffusion into the contact lens, and this publication does not attempt to embed the dye into the contact lens via any other process.

[0007] However, improvements over the prior art tools are needed. Summary of the Invention [Means for solving the problem]

[0008] The present disclosure provides methods and materials for filtering light in selected spectral regions (e.g., the green region) using nanoparticles for increased control. Selective light blocking in the green light range is desirable for a wide variety of soft biomaterials, including contact lenses. There is a strong need for biomaterials that can block specific ranges of wavelengths for safety, therapeutic, and cosmetic reasons.

[0009] One general embodiment includes a composition for light filtering, the composition also including a base material, a plurality of gold nanoparticles dispersed in the base material, the plurality of gold nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm and having a full width at half maximum (fwhm) of about 30 nm to about 100 nm, an anchoring mechanism dispersed in the base material, the anchoring mechanism can include a methacryloyl-derivatized monomer, and a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

[0010] One general embodiment includes a composition for light filtering, the composition including a base material, which may include a hema-based material, a plurality of metal nanoparticles dispersed in the base material, the plurality of metal nanoparticles exhibiting a peak light absorption value in a range of about 500 nm to about 600 nm, an anchoring mechanism dispersed in the base material, the anchoring mechanism may include a methacryloyl-derived monomer, and a nanoparticle coating material disposed on at least a portion of the plurality of metal nanoparticles.

[0011] One general embodiment includes a composition for light filtering, the composition including a base material, which may include a hema-based material, a plurality of plasmonic nanoparticles dispersed in the base material, the plurality of plasmonic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm, an anchoring mechanism dispersed in the base material, the anchoring mechanism may include a methacryloyl-derived monomer, and a nanoparticle coating material disposed on at least a portion of the plurality of plasmonic nanoparticles.

[0012] One general embodiment includes a contact lens comprising the composition for light filtering described herein, which is a free radical reaction product of a reactive mixture including one or more silicone-containing components and one or more hydrophilic components, and the contact lens has a water content of at least about 20 weight percent, preferably at least about 30 weight percent, and an oxygen permeability of at least about 80 Barrers, preferably at least about 100 Barrers. [Brief description of the drawings]

[0013] The following drawings illustrate generally, by way of example, but not by way of limitation, various examples contemplated in the present disclosure. [Figure 1A] FIG. 1B illustrates a surface modification strategy according to an embodiment of the present disclosure, including a reaction pathway for the methacrylation of poly(vinyl alcohol) (PVA). [Figure 1B] FIG. 1B illustrates a surface modification strategy according to an embodiment of the present disclosure, including a reaction pathway for the methacrylation of poly(vinyl alcohol) (PVA). [Diagram 2] 1 shows a Fourier-Transform Infrared (FTIR) spectrum of PVA conjugated with glycidyl methacrylate (MA) according to an embodiment of the present disclosure. [Diagram 3] Methacrylated poly(vinyl alcohol)-nanoparticles (PVA-NPs) after centrifugation. [Figure 4] The effect of hydrophilic-lipophilic balance (HLB) value on the stability of methacrylated poly(vinyl alcohol)-nanospheres (PVA-NS) is shown. [Diagram 5] The effect of polyvinylpyrrolidone (PVP) addition on the stability of methacrylated poly(vinyl alcohol)-nanospheres (PVA-NS) is shown. [Figure 6A] Methacrylated poly(vinyl alcohol)-nanospheres PVA-NS embedded in etafilcon A contact lenses (FIG. 6A) and the resulting absorbance spectrum (FIG. 6B) are shown. [Figure 6B] Methacrylated poly(vinyl alcohol)-nanospheres PVA-NS embedded in etafilcon A contact lenses (FIG. 6A) and the resulting absorbance spectrum (FIG. 6B) are shown. [Figure 7A] 13 shows the effect of methacrylation on light filtering spectra in solution according to embodiments of the present disclosure. [Figure 7B] 13 shows the effect of methacrylation on light filtering spectra in solution according to embodiments of the present disclosure. [Figure 8A] 8A shows PVA-MA nanoparticles (NPs) in a contact lens according to an embodiment of the present disclosure (FIG. 8B) and the resulting absorbance spectrum (FIG. 8A). [Figure 8B] 8A shows PVA-MA nanoparticles (NPs) in a contact lens according to an embodiment of the present disclosure (FIG. 8B) and the resulting absorbance spectrum (FIG. 8A). [Figure 9]1 illustrates sample preparation for inductively coupled plasma-mass spectrometry (ICP-MS) measurements according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Due to the spectral overlap between red and green cones in the human eye, selective blocking in the green light range has been shown to improve color discrimination in people with red-green color vision deficiency. Furthermore, the human eye is most sensitive to green light and can be damaged by long-term exposure to green light. Due to the differences between individuals with color vision deficiency and related symptoms, it may be desirable to design light filtering materials in a way that allows control and flexibility in both peak absorbance and bandwidth (e.g., full width at half maximum (FWHM)) to adapt light filtering to specific target regions.

[0015] Stability and retention of light filtering materials embedded in contact lenses is desirable. Such materials may need to be handled and worn regularly by humans and stored for long periods of time without loss of functionality. As a result, the light filtering material must be integrated within the selected biomaterial and must withstand curing and sterilization, as well as long-term storage. Curing and sterilization may include ultraviolet (UV) exposure and autoclaving, respectively.

[0016] Considering the aforementioned concerns, requirements for light filtering materials include, but are not limited to, specificity for certain wavelengths in the green light region, flexibility in terms of peak absorbance and full width at half maximum (FWHM), and long term stability and retention.

[0017] Although approaches to selective light filtering in the green region exist, there is no solution that can be fully integrated into biomaterials, can be tuned to different wavelengths of interest without chemically modifying the material, can withstand long-term storage and autoclaving, and can be readily adopted commercially.

[0018] The present disclosure relates to light blocking materials. The present disclosure further relates to biomaterial integration of light blocking materials. The integration method may include a method of light blocking materials for use in contact lenses. The present disclosure addresses a significant gap in current light blocking technology and materials for contact lenses. The method of providing light blocking materials for biomaterial integration may include nanoparticles (e.g., gold nanoparticles). The nanoparticles may include a particular shape. Such methods may further include a hydrogel. The hydrogel may immobilize the nanoparticles. Such methods may further include an anchoring mechanism. The anchoring mechanism may conjugate the nanoparticles to the biomaterial. Such methods may further include a nanoparticle coating material. The nanoparticle coating material may stabilize selected nanoparticles. The nanoparticle coating material may further support the anchoring mechanism.

[0019] The present disclosure relates to nanoparticle coating materials. The nanoparticle coating materials may include a stabilization mechanism. The nanoparticle coating materials may include a polymer. The polymer may connect aspects of the disclosed light blocking materials. Such connections may function by stabilizing selected nanoparticles. The nanoparticle coating materials may be further conjugated to an anchoring mechanism.

[0020] The present disclosure relates to nanoparticles. The nanoparticles may include gold nanoparticles, metal nanoparticles, or plasmonic nanoparticles, or combinations thereof. The gold nanoparticles may range in size from about 1 nm up to about 99 nm. The gold nanoparticles may include a variety of shapes, including but not limited to spheres, rods, bipyramids, stars, and other shapes known in the art. The absorbance profile of gold nanoparticles is directly dependent on the morphology. The morphology may include size and shape. The nanoparticles may be modified to tailor the light filtering spectrum of the final product. Such modifications may include changing the morphology. The morphology may be altered to allow the nanoparticles to block in the range of about 500 nm up to about 600 nm with a full width at half maximum (FWHM) of about 30 nm up to about 100 nm. The nanoparticles may block light by absorbing at defined wavelengths via localized surface plasmon resonance (LSPR).

[0021] The present disclosure relates to biomaterials. Such biomaterials may include gel-like biomaterials. The gel-like biomaterials may be medical devices. The gel-like biomaterials may include hydrogels. As a non-limiting example, the hydrogels may include contact lenses. Such contact lenses may include hydroxyethylmethacrylate (HEMA)-based UV-curable contact lens hydrogels (e.g., etafilcon A). The hydrogels may include other such monomer mixtures that further include primarily HEMA with other methacrylate and ethylene glycol monomers. Such monomer mixtures may further include Irgacure 2959, a UV-activated initiator. Such monomer mixtures may be cured in a mold by exposure to UV light for 20 minutes, and then incubated in hot water (60° C.) to remove the fully formed contact lens. Light filtering materials are added to the monomer mixtures prior to curing so that they can be chemically conjugated to the hydrogel matrix.

[0022] The present disclosure relates to a fixation mechanism. Fixation of nanoparticles to hydrogels by fixation mechanisms can allow for long-term stability after high stress processes. High stress processes can include increased thermal, mechanical, or other known stress factors. As a non-limiting example, the high stress process can include autoclaving. The fixation mechanism can allow for long-term stability after autoclaving. This can be facilitated by fixation mechanisms that chemically bond (i.e., conjugate) gold nanoparticles to biomaterials. Such conjugation can prevent leaching under thermal or mechanical stress. As a non-limiting example, the fixation mechanism can include glycidyl methacrylate, although other compounds known in the art can be used. The use of methacrylates can facilitate integration of biomaterials. As a further non-limiting example, hydrogels that include an etafilcon A monomer mixture can include multiple methacrylates. This can allow the methacrylate fixation mechanism to fully integrate into the contact lens.

[0023] The present disclosure relates to nanoparticle coating materials. The nanoparticle coating materials may include a stabilization mechanism. The nanoparticle coating materials may connect aspects of the disclosed light blocking materials. Such connections may function by stabilizing selected nanoparticles. The nanoparticle coating materials may further be conjugated to an anchoring mechanism. The nanoparticle coating materials may include a polymer. The polymer may further include poly(vinyl alcohol) (PVA). The nanoparticle coating materials may stabilize gold nanoparticles. Stabilization may be achieved through conjugation to groups in the anchoring mechanism via transesterification. In such embodiments, the nanoparticle coating materials may be conjugated to the nanoparticles and the anchoring mechanism simultaneously. Conjugation to the anchoring mechanism may be facilitated by non-thiolated nanoparticle coatings, although other conjugation methods are known in the art. Such conjugation may provide colloidal and thermal stability of the nanoparticles. PVA is also compatible with exemplary hydrogel materials and does not impair transparency, stability, or biocompatibility.

[0024] The present disclosure relates to the use of gold nanoparticles. The gold nanoparticles may be embedded in a hydrogel to form a light blocking material. The light blocking material may achieve specific light filtering in the green visible light region (about 500 nm up to about 600 nm). The use of gold nanoparticles may improve color perception and color discrimination in people with red-green color vision deficiency. The use of specific gold nanoparticle sizes and shapes, as well as combinations of the specific gold nanoparticle sizes and shapes, may generate customizable light filtering spectra. Such light filtering spectra may fall within the green visible light range. The present disclosure further relates to the integration of gold nanoparticles in biomaterials. The biomaterial may include a hydrogel. The integration may be achieved via a multifunctional polymer.

[0025] The present disclosure relates to biomaterials. The biomaterials may include hydrogels. The hydrogels may be included in customized cosmetic or therapeutic contact lenses. The present disclosure further relates to chemical integration into hydrogels. Chemical integration may provide light filtering materials that may be immobilized and selectively patterned. The present disclosure relates to integration of light filtering materials into a variety of different biomaterials. Multiple gold nanoparticles of different sizes and shapes may be combined. Such combinations may provide the ability to generate end products with tunable and highly complex light filtering spectra within the green visible light range. The present disclosure relates to methods of controlling the shape and size of gold nanoparticles to generate highly specific light filtering spectra. Highly specific light filtering spectra may provide the ability to block green light and improve color perception for people with color blindness. Improved color perception may be achieved by artificially improving the resolution between red and green cones. The present disclosure relates to long-term stability and integration of materials. This may enable passive sensing applications and / or labeling of commercial products.

[0026] The present disclosure may include additional features. The present disclosure may include the use of different monomers to integrate with different biomaterials. The present disclosure may further include gold nanoparticles of different shapes to block different target areas. The present disclosure may further include the integration of two or more populations of gold nanoparticles to block different areas at once. Such loading may include different loading amounts of two or more populations of gold nanoparticles to adjust color intensity.

[0027] The present disclosure relates to base materials. Such base materials may include biomaterials, biomaterial matrices, hydrogels, and other such materials known in the art. Non-limiting examples of base materials are described below. The present disclosure further relates to nanoparticles. Such nanoparticles may include gold. Gold nanoparticles may be grown from gold seeds, although other synthesis methods are known in the art. Such nanoparticles may include shapes. Such shapes may include spherical shapes. Alternative shapes are known in the art and may include, but are not limited to, cubic shapes, nanorod shapes, octahedral shapes, decahedral shapes, cuboctahedral shapes, tetrahedral shapes, rhombic dodecahedral shapes, truncated bisquare prism shapes, or truncated double tetrahedral shapes. Such gold nanoparticles may block various ranges of light. As a non-limiting example, gold nanoparticles may block light in the range of about 500 nm up to about 600 nm. Alternative ranges exist and may include, but are not limited to, about 500 nm up to about 675 nm, about 500 nm up to about 650 nm, about 500 nm up to about 625 nm, about 525 nm up to about 600 nm, about 550 nm up to about 600 nm, or about 575 nm up to about 600 nm. The present disclosure further relates to nanoparticle coating materials (i.e., stabilization mechanisms). Such stabilization mechanisms may include polymers. Such polymers may include various molecular weights. Such polymers may include polyvinyl alcohol (PVA). Alternative polymers are known in the art and may include, but are not limited to, poly(ethylene glycol) (PEG), polycarbonate, polyvinylpyrrolidone (PVP), polystyrene (PS), polycaprolactone (PCL), ethylene oligomers or polyethylene (PE), polypropylene (PP), and poly(methyl methacrylate) (PMMA), as well as copolymers or blends thereof. Such polymers may include molecular weights from about 10 kDa up to about 1300 kDa. The present disclosure relates to methods of attaching gold nanoparticles to a stabilization mechanism.The attachment may occur via chemical conjugation. Such attachment may be selective. Such attachment may improve the colloidal and / or thermal stability and biocompatibility of the nanoparticles. The present disclosure relates to an anchoring mechanism. Such an anchoring mechanism may include a methacrylate. Such an anchoring mechanism may include a methacryloyl-derived monomer. Such an anchoring mechanism may include glycidyl methacrylate (GMA). Such a methacrylate may further include a thiolated methacrylate dimer. Such a thiolated methacrylate dimer may include bis(2-methacryloyl)oxyethyl disulfide (i.e., DSDMA), although other examples exist. Other such examples include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glycerol trimethacrylate, methacryloxyethyl vinylcarbonate (HEMAVc), allyl methacrylate, methylene bisacrylamide (methylene Bisacrylamide (MBA), polyethylene glycol dimethacrylate, 1,4-phenylene diacrylate, 1,4-phenylene dimethacrylate, 2,2-bis(4-methacryloxyphenyl)-propane, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)-phenyl]propane, and 4-vinylbenzyl methacrylate. The anchoring mechanism may also include a polymer. The present disclosure relates to a method of binding gold nanoparticles to the anchoring mechanism. The binding may occur via chemical conjugation. Such binding may be selective.Such binding may improve the colloidal and / or thermal stability, as well as biocompatibility, of the nanoparticles. In such binding, the anchoring mechanism attached to the gold nanoparticles may further be attached to the nanoparticle coating material. Such binding may occur via transesterification, although other methods of attachment are known in the art. The present disclosure further relates to a method of attaching the anchoring mechanism to a base material. The base material may include a biomaterial as described above. The conjugation of the anchoring mechanism to the gold nanoparticles and base material may include cross-linking. Such cross-linking may facilitate the integration of the nanoparticles into the base material.

[0028] The present disclosure relates to compositions, which may include a base material, nanoparticles, nanoparticle coating materials (i.e., stabilizing mechanisms), anchoring mechanisms, or any combination thereof. Nanoparticle light absorption may be tuned through tuning nanoparticle morphology. Morphology may be tuned by configuring the aspect ratio, defined by the quotient of the major and minor axis lengths, volume, sharpness, and / or other related characteristics. The aspect ratio may be tuned from about 1.9 up to about 2.9, although other such aspect ratios may be possible. As non-limiting examples, the aspect ratio can be in the range of about 1.9 up to about 2.8, about 1.9 up to about 2.7, about 1.9 up to about 2.6, about 1.9 up to about 2.5, about 1.9 up to about 2.4, about 1.9 up to about 2.3, about 1.9 up to about 2.2, about 1.9 up to about 2.1, about 1.9 up to about 2.0, about 2.0 up to about 2.8, about 2.0 up to about 2.7, about 2.0 up to about 2.6, about 2.0 up to about 2.5, about 2.0 up to about 2.4, about 2.0 up to about 2.3, about 2.0 up to about 2.2, or about 2.0 up to about 2.1. 3 ~Maximum approx. 30,000nm 3 Although other such volumes may be possible, as a non-limiting example, the volume may be adjusted to about 1,250 nm 3 ~Maximum approx. 30,000nm 3 , about 2,250nm 3 ~Maximum approx. 30,000nm 3 , about 3,250nm 3 ~Maximum approx. 30,000nm 3, approximately 4,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 5,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 6,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 7,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 8,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 9,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 10,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 11,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 12,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 13,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 14,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 15,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 16,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 17,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 18,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 19,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 20,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 21,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 22,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 23,250 nm 3 ~ up to approximately 30,000 nm 3 , approximately 24,250 nm 3 ~ up to approximately 30,000 nm 3, about 25,250nm 3 ~Maximum approx. 30,000nm 3 , about 26,250nm 3 ~Maximum approx. 30,000nm 3 , about 27,250nm 3 ~Maximum approx. 30,000nm 3 , about 28,250nm 3 ~Maximum approx. 30,000nm 3 , 又は Approximately 29,250nm 3 ~Maximum approx. 30,000nm 3 can be adjusted to.

[0029] The final light blocking (light filtering) profile can be tailored through the use of various nanoparticles, nanoparticle coating materials (i.e., stabilization features), anchoring features, and combinations thereof. Such tailoring can result in full width at half maximum (FWHM) or "bandwidth" values ​​of about 30 nm up to about 100 nm. As non-limiting examples, FWHM values ​​can range from about 40 nm up to about 100 nm, about 50 nm up to about 100 nm, about 60 nm up to about 100 nm, about 70 nm up to about 100 nm, about 80 nm up to about 100 nm, or about 90 nm up to about 100 nm.

[0030] There are additional capabilities associated with the present disclosure. The present disclosure further relates to various polymers that can be grafted onto the surface of the nanoparticles. The use of various polymers can allow the integration of the nanoparticles into various biomaterials. Such nanoparticles can include various shapes. Thus, the present disclosure is independent of a particular biomaterial. Furthermore, the present disclosure relates to the incorporation of nanoparticles of various shapes, further including various stabilization mechanisms, into virtually any biomaterial of interest. Non-limiting examples of biomaterials can include hydrogel or silicone hydrogel materials suitable for use in forming soft contact lenses. Such materials are known in the art and include, but are not limited to, Group 1 - low moisture (<50% H2O) non-ionic hydrogel polymers (e.g., tefilcon, tetrafilcon A, clofilcon, herfilcon A, herfilcon B, mafilcon, polymacon, hyoxifilcon B); Group 2 - high moisture (>50% H2O) non-ionic hydrogel polymers (e.g., sarfilcon A, lidofilcon A, lidofilcon B, netrafilcon A, hefilcon B, alfafilcon A, omafilcon A, omafilcon B, vasafilcon A, hyoxifilcon A, hyoxifilcon D, nelfilcon A, hilafilcon A, hilafilcon B, acofilcon A, nesofilcon A); Group 3 - low moisture (<50% H2O) ionic hydrogel polymers (e.g., bufilcon A, del Group 4 - High moisture (>50% H2O) ionic hydrogel polymers (e.g., Bufilcon A, Perfilcon A, Etafilcon A, Focofilcon A, Ocfilcon A, Ocfilcon B, Ocfilcon C, Ocfilcon D, Ocfilcon E, Ocfilcon F, Femfilcon A, Metafilcon A, Metafilcon B, Bifilcon A); and Silicone hydrogel polymers (e.g., Lotrafilcon A, Lotrafilcon B, Galifilcon A, Senofilcon A, Senofilcon C, Sifilcon A, Comfilcon A, Enfilcon A, Balafilcon A, Delefilcon A, Narafilcon B, Narafilcon A, Stenfilcon A, Somofilcon A, Funfilcon A, Samfilcon A, Elastofilcon).

[0031] definition It is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description, as the invention is capable of other embodiments and of being practiced or carried out in various ways using the teachings set forth herein.

[0032] The following definitions are provided for terms used in this disclosure.

[0033] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The definition of polymer is consistent with the definition disclosed in Compendium of Polymer Terminology and Nomenclature, IUPAC Recommendations 2008, edited by: Richard G. Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess, Tatsuki Kitayama, and W. Val Metanomski. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0034] As used herein, the term "(meth)" refers to optional methyl substitution. Thus, terms such as "(meth)acrylate" refer to both methacrylate and acrylate.

[0035] The term "individual" includes humans and vertebrate animals.

[0036] The term "ophthalmic device" refers to any device that resides in or on the eye or any part of the eye, including the ocular surface. These devices can provide optical correction, appearance enhancement, vision enhancement, therapeutic effects (e.g., as a dressing), or delivery of active components such as pharmaceutical and nutraceutical components, or any combination of the foregoing. Examples of ophthalmic devices include, but are not limited to, lenses, optics, and ocular inserts (including, but not limited to, punctal plugs). "Lens" includes soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. Ophthalmic devices can include contact lenses.

[0037] The term "contact lens" refers to an ophthalmic device that can be placed on the cornea of ​​an individual's eye. A contact lens can provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of drugs or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet light filtering, reduction of visible light or glare, or any combination thereof. A contact lens can be of any suitable material known in the art and can be a soft lens, a hard lens, or a hybrid lens that contains at least two separate portions with different physical, mechanical, or optical properties, such as modulus of elasticity, water content, light transmission, or a combination thereof.

[0038] The ophthalmic devices and lenses of the present invention may be composed of silicone hydrogels or traditional hydrogels. Silicone hydrogels typically contain at least one hydrophilic monomer and at least one silicone-containing component covalently bonded to each other in the cured device.

[0039] As used herein, the terms "physisorption" or "chemisorption" refer to the process by which atoms, molecules, or particles enter the bulk phase of a gas, liquid, or solid material and become incorporated within the volume. Absorption in this manner can be driven by solubility, concentration gradients, temperature, pressure, and other driving forces known in the art.

[0040] As used herein, "adsorption" is defined as the deposition of a species onto a surface. A species that is adsorbed onto a surface is known as an adsorbate, and the surface on which adsorption occurs is known as an adsorbent. Examples of adsorbents may include clays, silica gels, colloids, metals, nanoparticles, etc. Adsorption may occur via chemical or physical adsorption. Chemical adsorption may occur when the adsorbate is held to the adsorbent via chemical bonds, while physical adsorption may occur when the adsorbate is bound to the adsorbent via weak van der Waals forces.

[0041] As used herein, "antimicrobial" means intended to kill or reduce the harmful effects of bacteria.

[0042] As used herein, "colloid" refers to a dispersion in which one substance is suspended in another. Many examples of colloids in the art contain polymers. In this aspect, the polymer may be adsorbed or chemically bonded to the surface of the particles suspended in the colloid, or the polymer may be free to move in the colloid suspension. The presence of polymers on the particles in suspension can be directly related to "colloidal stability," which refers to the tendency of a colloidal suspension to undergo settling. Sedementation results in the falling of particles from the colloid. Polymers adsorbed or chemically bonded to a particle can affect its colloidal stability.

[0043] As used herein, the term "diffusion" refers to a process in which there is a net flow of material from one region to another. An example of such a process is "surface diffusion," in which particles move from one area of ​​the surface of an object to another area of ​​the same surface. This can be caused by thermal stress or applied pressure.

[0044] As used herein, "surfactant" refers to a substance that, when added to a liquid, reduces its surface tension, thereby increasing its spreading and wetting properties. A typical surfactant may be partially hydrophilic and partially lipophilic.

[0045] As used herein, the term "wetting agent" refers to a material that allows a liquid to spread more easily on or "wet" a surface. The high surface tension of water causes problems in many industrial processes in which water-based solutions are used because the solutions are unable to wet the surface to which they are applied. Wetting agents are commonly used to reduce the surface tension of the water and thus aid in the spreading of water-based solutions.

[0046] "Target polymer" refers to a polymer that has been synthesized from a reactive monomer mixture that includes monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.

[0047] The term "polymerizable compound" means a compound that contains one or more polymerizable groups. This term includes, for example, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.

[0048] A "polymerizable group" is a group capable of undergoing free radical and / or cationic polymerization, e.g., chain growth polymerization, such as a carbon-carbon double bond that can polymerize when subjected to radical polymerization initiation conditions. Non-limiting examples of free radical polymerizable groups include (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, O-vinyl carbamates, O-vinyl carbonates, and other vinyl groups. Preferably, the free radical polymerizable group comprises (meth)acrylates, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, and styryl functional groups, and mixtures of any of the foregoing. More preferably, the free radical polymerizable group comprises (meth)acrylates, (meth)acrylamides, and mixtures thereof. The polymerizable group may be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamides may be bonded to hydrogen, or the hydrogen may be replaced by alkyl or cycloalkyl, which may themselves be further substituted.

[0049] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension, and emulsion, as well as any of the controlled radical polymerization techniques, such as stable free radical polymerization, nitric oxide mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium mediated living radical polymerization, etc.

[0050] A "monomer" is a monofunctional molecule that can undergo chain growth polymerization, particularly free radical polymerization, thereby creating repeat units within the chemical structure of a target macromolecule. Some monomers have difunctional impurities that can act as crosslinkers. A "hydrophilic monomer" is also a monomer that, when mixed with deionized water at a concentration of 5 weight percent at 25°C, gives a clear, single-phase solution. A "hydrophilic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that, when mixed with deionized water at a concentration of 5 weight percent at 25°C, gives a clear, single-phase solution. A "hydrophobic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that is slightly soluble or insoluble in deionized water at 25°C.

[0051] A "polymer" is an organic compound having a number average molecular weight greater than 1500 and may be reactive or non-reactive.

[0052] A "macromonomer" or "macromer" is a polymer having one group capable of undergoing chain growth polymerization, particularly free radical polymerization, thereby creating repeat units within the chemical structure of a target macromolecule. Generally, the chemical structure of a macromer is different from the chemical structure of the target macromolecule, i.e., the repeat units of the pendant group of the macromer are different from the repeat units of the target macromolecule or its backbone. The only difference between a monomer and a macromer is one of the chemical structure of the pendant group, the molecular weight, and the molecular weight distribution. As a result, and as used herein, the patent literature sometimes defines a monomer as a polymerizable compound having a relatively low molecular weight of about 1,500 daltons or less, which essentially includes some macromers. Specifically, monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (mPDMS) and mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (OH-mPDMS) may be referred to as monomers or macromers. Additionally, the patent literature sometimes defines macromers as having one or more polymerizable groups, essentially expanding the general definition of macromer to include prepolymers. As a result, and as used herein, difunctional and multifunctional macromers, prepolymers, and crosslinkers may be used interchangeably.

[0053] A "silicone-containing component" is a monomer, macromer, prepolymer, crosslinker, initiator, additive, or polymer in the reactive mixture that has at least one silicon-oxygen bond, typically in the form of a siloxy group, a siloxane group, a carbosiloxane group, and mixtures thereof.

[0054] Examples of silicone-containing components that are useful in the present invention are disclosed in U.S. Pat. Nos. 3,808,178, 4,120,570, 4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, 5,740,533, 5,034,461, 5,070,215, 5,244,981, ,962,548, 5,965,631, 5,998,498, 6,367,929, 6,822,016, 6,943,203, 6,951,894, 7,052,131, No. 7,247,692, No. 7,396,890, No. 7,461,937, No. 7,468,398, No. 7,538,146, No. 7,553,880, No. 7,572,841, No. 7,666,92 No. 1, No. 7,691,916, No. 7,786,185, No. 7,825,170, No. 7,915,323, No. 7,994,356, No. 8,022,158, No. 8,163,206, No. 8,273 ,802, 8,399,538, 8,415,404, 8,420,711, 8,450,387, 8,487,058, 8,568,626, 8,937,110, 8, Nos. 937,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825, 9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544, 9,297,928, 9,297,929, and European Patent No. 080539. These patents are incorporated herein by reference in their entirety.

[0055] A "polymer" is a target macromolecule composed of repeating units of the monomers used during polymerization. Exemplary polymers may include polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polycarbonate, and other polymers known in the art.

[0056] As used herein, the term "thermoplastic" refers to the property of a polymer that it can be melted, solidified, and then successfully melted and solidified again. This process can be repeated several times for a thermoplastic polymer without loss of functionality.

[0057] As used herein, the term "thermosetting" refers to the property of a polymer whereby a thermosetting polymer forms a well-defined, irreversible chemical network that tends to grow in three dimensions through the process of curing, which can occur either due to heating or through the addition of a curing agent, thus causing crosslinking between its chemical components and giving the thermoset a strong, rigid structure that can be added to other materials to increase their strength. Once a thermosetting polymer forms a network during curing, the polymer cannot be recurred to solidify in a different way.

[0058] A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of compositionally distinct blocks or segments. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb or graft copolymer" is made from at least one macromer.

[0059] A "repeating unit" is the smallest grouping of atoms within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0060] An "initiator" is a molecule that is decomposable into radicals that can subsequently react with monomers to initiate a free radical polymerization reaction. Thermal initiators decompose at a certain rate depending on the temperature, typical examples being azo compounds such as 1,1'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid), peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide, peracids such as peracetic acid and potassium persulfate, and various redox systems. Photoinitiators decompose by a photochemical process, typical examples being derivatives of benzil, benzoin, acetophenone, benzophenone, camphorquinone, and mixtures thereof, as well as various monoacyl and bisacylphosphine oxides, and combinations thereof.

[0061] A "crosslinker" is a di- or polyfunctional monomer or macromer that can undergo free radical polymerization at two or more positions on the molecule, thereby creating branch points and polymer networks. Common examples are bis(2-methacryloyl)oxyethyl disulfide (DSDMA), cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, and the like.

[0062] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can be further reacted to form a polymer.

[0063] A "polymer network" is a cross-linked polymer that can swell but cannot be dissolved in a solvent. A "hydrogel" is a polymer network that typically absorbs at least 10 weight percent water and swells in water or an aqueous solution. A "silicone hydrogel" is a hydrogel made from at least one silicone-containing component with at least one hydrophilic component. The hydrophilic component may also include a non-reactive polymer.

[0064] "Conventional hydrogel" refers to a polymer network made from components that do not have any siloxy, siloxane, or carbosiloxane groups. Conventional hydrogels are prepared from reactive mixtures that include hydrophilic monomers. Examples include 2-hydroxyethyl methacrylate ("HEMA"), N-vinyl pyrrolidone ("NVP"), N,N-dimethylacrylamide ("DMA"), or vinyl acetate. U.S. Patent Nos. 4,436,887, 4,495,313, 4,889,664, 5,006,622, 5,039459, 5,236,969, 5,270,418, 5,298,533, 5,824,719, 6,420,453, 6,423,761, 6,767,979, 7,934,830, 8,138,290, and 8,389,597 disclose the formation of conventional hydrogels. Commercially available conventional hydrogels include, but are not limited to, etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymacon, and vifilcon (including all variations thereof).

[0065] "Silicone hydrogel" refers to a polymer network made from at least one hydrophilic component and at least one silicone-containing component. Examples of silicone hydrogels include acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, falcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, and cyclohexyl esters. con, narafilcon, riofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon, including all variations thereof, as well as the compounds described in U.S. Patent Nos. 4,659,782, 4,659,783, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998, No. 498, No. 6,087,415, No. 5,760,100, No. 5,776,999, No. 5,789,461, No. No. 5,849,811, No. 5,965,631, No. 6,367,929, No. 6,822,016, No. 6,867 ,245, No.6,943,203, No.7,247,692, No.7,249,848, No.7,553,880, No. 7,666,921, No. 7,786,185, No. 7,956,131, No. 8,022,158, No. 8,27 No. 3,802, No. 8,399,538, No. 8,470,906, No. 8,450,387, No. 8,487,058 , No. 8,507,577, No. 8,637,621, No. 8,703,891, No. 8,937,110, No. 8,9 No. 37,111, No. 8,940,812, No. 9,056,878, No. 9,057,821, No. 9,125,808 No. 9,140,825, No. 9,156,934, No. 9,170,349, No. 9,244,196, No. 9,Nos. 244,197, 9,260,544, 9,297,928, and 9,297,929, as well as silicone hydrogels such as those prepared in WO 03 / 22321, WO 2008 / 061992, and U.S. Patent Application Publication No. 2010 / 0048847, which are incorporated herein by reference in their entireties.

[0066] As used herein, "gel-like" refers to a material having properties generally associated with those associated with gels. "Gel" can refer to a cohesive mass consisting of a liquid in which the particles are either dispersed or arranged in a fine network throughout the mass. Gels can be particularly elastic or substantially solid and rigid (e.g., silica gel appears as a rigid particle). Gels can also be viewed as colloids in which the liquid medium has become sufficiently viscous to behave more or less like a solid.

[0067] An "interpenetrating polymer network" includes two or more networks that are at least partially entangled on a molecular scale, but are not covalently bonded to each other and cannot be separated without a blocking chemical bond. A "semi-interpenetrating polymer network" includes one or more networks and one or more polymers that are characterized by some intermixing at the molecular level between at least one network and at least one polymer. A mixture of different polymers is a "polymer blend." Although semi-interpenetrating networks are technically polymer blends, in some cases the polymers are entangled in such a way that they cannot be easily removed.

[0068] The terms "reactive mixture" and "reactive monomer mixture" refer to a mixture of components (both reactive and non-reactive) that, when mixed together and subjected to polymerization conditions, form conventional or inventive silicone hydrogels and contact lenses made therefrom. The reactive monomer mixture may include reactive components such as monomers, macromers, prepolymers, crosslinkers, and initiators, additives such as wetting agents, release agents, polymers, dyes, light absorbing compounds, e.g., UV absorbers, pigments, dyes, and photochromic compounds (any of which may be reactive or non-reactive but can be retained in the resulting biomedical device), as well as pharmaceutical and nutraceutical compounds, and an optional diluent. It will be understood that a variety of additives may be added based on the biomedical device to be made and its intended use. The concentrations of the components of the reactive mixture are expressed as a weight percentage of all components in the reactive mixture, excluding the diluent. If diluents are used, their concentrations are expressed as a weight percentage based on the amount of all components and diluent in the reactive mixture.

[0069] A "reactive component" is a component of the reactive mixture that becomes part of the chemical structure of the polymer network of the resulting hydrogel by covalent bonds, hydrogen bonding, electrostatic interactions, formation of an interpenetrating polymer network, or any other means.

[0070] The term "silicone hydrogel contact lenses" refers to hydrogel contact lenses that include at least one silicone-containing component. Silicone hydrogel contact lenses generally have increased oxygen permeability compared to traditional hydrogels. Silicone hydrogel contact lenses function by both their water content and polymer content to deliver oxygen to the eye.

[0071] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0072] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0073] As used herein, the term "alkyl" refers to an unsubstituted or substituted straight or branched chain alkyl group containing the indicated number of carbon atoms. If no number is indicated, the alkyl (optionally including any substituents on the alkyl) may contain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms, alternatively 1 to 7 carbon atoms, or alternatively 1 to 4 carbon atoms. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examples of substituents on the alkyl include one, two, or three groups independently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halogen, phenyl, benzyl, thiol, and combinations thereof. "Alkylene" refers to a divalent alkyl group, e.g., -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and -CH 2 CH 2 CH 2 CH 2 - means.

[0074] "Haloalkyl" refers to an alkyl group, as defined above, substituted with one or more halogen atoms, where each halogen is independently F, Cl, Br, or I. A preferred halogen is F. Preferred haloalkyl groups contain 1 to 6 carbons, more preferably 1 to 4 carbons, and even more preferably 1 to 2 carbons. "Haloalkyl" refers to -CF 3 -or-CF 2 CF 3-. "Haloalkylene" includes perhaloalkyl groups such as -CH 2 CF 2 - means a divalent haloalkyl group such as -.

[0075] "Cycloalkyl" refers to an unsubstituted or substituted cyclic hydrocarbon containing the indicated number of ring carbon atoms. If no number is indicated, the cycloalkyl may contain from 3 to 12 ring carbon atoms. Preferably, C 3 ~C 8 Cycloalkyl groups, C 3 ~C 7 Cycloalkyl, more preferably C 4 ~C 7 Cycloalkyl, even more preferably C 5 ~C 6 Cycloalkyl. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on cycloalkyl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Cycloalkylene" refers to a divalent cycloalkyl group, such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

[0076] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system as defined above in which at least one ring carbon is replaced with a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring is optionally fused or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or phenyl rings. Preferred heterocycloalkyl groups have 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members. Heterocycloalkylene refers to a divalent heterocycloalkyl group.

[0077] "Aryl" refers to an unsubstituted or substituted aromatic hydrocarbon ring system containing at least one aromatic ring. The aryl group contains the indicated number of ring carbon atoms. If no number is indicated, the aryl may contain 6 to 14 ring carbon atoms. The aromatic ring may be optionally fused or otherwise attached to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl. Examples of substituents on an aryl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Arylene" refers to a divalent aryl group, such as 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0078] "Heteroaryl" refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom is replaced with a heteroatom selected from nitrogen, oxygen, and sulfur. The heteroaryl ring may be fused or otherwise bonded to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, and thienyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0079] "Alkoxy" refers to an alkyl group attached to the parent molecular moiety through an oxygen bridge. Examples of alkoxy groups include, for example, methoxy, ethoxy, propoxy, and isopropoxy. "Aryloxy" refers to an aryl group attached to the parent molecular moiety through an oxygen bridge. Examples include phenoxy. "Cyclic alkoxy" refers to a cycloalkyl group attached to the parent moiety through an oxygen bridge.

[0080] "Alkylamine" refers to an alkyl group attached to the parent molecular moiety through an -NH bridge. Alkyleneamines are those that are linked to the parent molecular moiety through a -CH 2 CH 2 It means a divalent alkylamine group such as NH-.

[0081] "Ester" refers to a class of organic compounds having the general formula RCOOR', where R and R' are any organic linking group. R and R' may be selected from functional groups including alkyl, substituted alkyl, alkylene, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, alkylamine, siloxanyl, silyl, alkyleneoxy, oxaalkylene, and the like. Definitions of the above functional groups are provided herein.

[0082] As used herein, "esterification" refers to a reaction that produces an ester. This reaction often involves an alcohol and a Bronsted acid (e.g., carboxylic acid, sulfuric acid, or phosphoric acid). Additionally, the term "transesterification" refers to a reaction in which an alcohol molecule reacts with an existing ester molecule to form a new ester. In some embodiments, transesterification can be mediated by other compounds, such as carbonyldiimidazole.

[0083] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Thus, for example, a siloxanyl group refers to a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanyl compound refers to a compound having at least one Si-O-Si group. "Siloxanyl" refers to monomeric (e.g., Si-O-Si) as well as oligomeric / polymeric structures (e.g., -[Si-O] n (wherein n is 2 or 3 or more). Each silicon atom in the siloxanyl group is independently selected to complete their valence. A Group (R A is replaced by (as defined in options (b) to (i) of Formula A).

[0084] "Cyril" is a compound of the formula R 3 "Siloxy" refers to the structure of Si-, 3 The formula refers to the structure of Si-O-, where each R in silyl or siloxy is trimethylsiloxy, C 1 ~C 8 Alkyl (preferably C 1 ~C 3 alkyl, more preferably ethyl or methyl), and C 3 ~C 8 cycloalkyl.

[0085] "Alkyleneoxy" refers to a group having the general formula -(alkylene-O) p -or-(O-alkylene) p -, where alkylene is as defined above, p is 1 to 200, or 1 to 100, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 10, and each alkylene is independently optionally substituted with one or more groups independently selected from hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl, carboxyl, and combinations thereof. When p is greater than 1, each alkylene may be the same or different, and the alkyleneoxy may be in a block or random configuration. When the alkyleneoxy forms a terminal group in a molecule, the terminus of the alkyleneoxy may be, for example, a hydroxyl or alkoxy (e.g., HO-[CH 2 CH 2 O] p - or CH 3 O-[CH 2 CH 2 O] p Examples of alkyleneoxy include polymethyleneoxy, polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0086] "Oxaalkylene" refers to one or more non-adjacent CH 2 The group is replaced by an oxygen atom, -CH 2 CH 2OCH(CH 3 )CH 2 -, etc. "Thiaalkylene" refers to an alkylene group as defined above, such as one or more non-adjacent CH 2 The group is substituted with a sulfur atom, -CH 2 CH 2 SCH(CH 3 )CH 2 -, etc.

[0087] The term "linking group" refers to a moiety that connects a polymerizable group to a parent molecule. The linking group may be any moiety that does not unnecessarily interfere with the polymerization of the compound of which it is a part. For example, the linking group may be a bond or may be one or more of an alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, carboxylate (-CO 2 -), disulfide, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or more halo groups, e.g., -OCF 2 -, -OCF 2 CF 2 -, -OCF 2 CH 2 -), siloxanyl, alkylenesiloxanyl, thiol, or combinations thereof. The linking group may be optionally substituted with one or more substituents. Suitable substituents include alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, CH 3They may include those independently selected from O-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy- (where there may be more than one alkyleneoxy group, and each methylene in the alkylene and alkyleneoxy is independently optionally substituted with hydroxyl), ether, amine, carbonyl, carbamate, and combinations thereof. The linking group may also be substituted with a polymerizable group (in addition to the polymerizable group to which it is attached), such as (meth)acrylate.

[0088] Preferred linking groups include C 1 ~C 8 Alkylene (preferably C 2 ~C 6 alkylene) and C 1 ~C 8 Oxaalkylene (preferably C 2 ~C 6 oxaalkylene), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Preferred linking groups include carboxylate, amide, C 1 ~C 8 Alkylene-carboxylate-C 1 ~C 8 Alkylene or C 1 ~C 8 Alkylene Amide-C 1 ~C 8 Also included is alkylene.

[0089] When the linking group is composed of a combination of moieties as described above (e.g., alkylene and cycloalkylene), the moieties may be present in any order. For example, in formula E below, when L is shown to be -alkylene-cycloalkylene-, Rg-L may be either Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Regardless, the order listed represents the preferred order in which the moieties appear in the compound, starting from the terminal polymerizable group (Rg) to which the linking group is attached. For example, in formula E, L and L 2and -L are preferably Rg-alkylene-cycloalkylene-, where -L 2 -Rg is preferably -cycloalkylene-alkylene-Rg.

[0090] As used herein, "oxidation" refers to a chemical process in which an atom of an element bonds with a more electronegative element, most commonly oxygen. In this process, the oxidized element increases its oxidation state, which represents the charge of the atom. Oxidation reactions are commonly combined with "reduction" reactions in which the oxidation state of the reduced atom is decreased.

[0091] As used herein, "immobilization" or "immobilization mechanism" refers to a process by which nanoparticles can be embedded in a colloidal or polymeric matrix. "Immobilization" can occur either chemically, via crosslinking of the nanoparticle to a member of the exemplary matrix, or physically, via entanglement of molecules bound to the surface of the nanoparticle with a member of the exemplary matrix.

[0092] As used herein, "visible spectrum" refers to the range of wavelengths within the electromagnetic spectrum, which range spans from approximately 380 nm to 700 nm. The visible spectrum can be broken down into different wavelength regions that correspond to colors, including red, orange, yellow, green, blue, indigo, and violet. Certain ranges of wavelengths within the visible spectrum are known to be damaging to the human eye.

[0093] As used herein, "ultraviolet (UV) spectrum" refers to the range of wavelengths within the electromagnetic spectrum, which range extends from approximately 10 nm to 400 nm.

[0094] As used herein, "ultraviolet (UV) irradiation" refers to exposure to electromagnetic waves falling within the wavelengths of the ultraviolet spectrum, and UV irradiation uses a selected time and intensity of exposure to achieve its effect, such as curing. UV irradiation can result in chemical changes (photocrosslinking, photooxidation, or photochemical reactions) or physical changes (such as surface morphology). Photochemical reactions caused by UV irradiation can be limited to the surface or can occur deep inside the bulk of the material (unlike plasma). Some exemplary UV irradiation sources can include continuous wave (CW) UV lamps with medium intensity light and pulsed lasers.

[0095] As used herein, "light absorption" is defined as the phenomenon whereby electrons absorb the energy of an incoming light wave (i.e., a photon) and change their energy state. For this to occur, the incoming light wave must be at or near the energy level of the electrons. The resulting absorption pattern characteristic of a given material can be displayed using an "absorption spectrum," which shows the change in absorbance of a sample as a function of the wavelength of the incident light, and can be measured using a spectrophotometer. Inherent in an "absorption spectrum" is an "absorption peak," a frequency or wavelength for a given sample that exhibits a maximum or highest spectral value of light absorption. With respect to light absorption at wavelengths of light corresponding to the visible spectrum, a material or substance that absorbs light waves of certain wavelengths of the visible spectrum may prevent an observer from seeing these wavelengths in the reflected light.

[0096] As used herein, "full width at half maximum (FWHM)" refers to a parameter commonly used to describe the width of a portion of a curve or function and may be used in relation to absorbance spectra. It is given by the distance between the points on the independent axis of the curve where the function reaches half of its maximum value on the dependent axis.

[0097] "Light filtering" may include absorbing, scattering, and / or extinguishing incident light. Light filtering may include the term "light blocking material." Light blocking may refer to a material that has the ability to absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum. Thus, the term "light blocking material" or "light filtering material" encompasses particles that absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum. The particles may be incorporated in various amounts into an optically transparent substrate to achieve an optically transparent material that exhibits a desired level of light blocking at one or more wavelengths or ranges of wavelengths in the electromagnetic spectrum. The percent blocking at a particular wavelength may be determined from the transmission spectrum of the material (blocking percentage=100-percent transmission (%T)).

[0098] As used herein, the term "light blocking profile" or "light blocking spectrum" refers to the absorption, scattering, and / or extinction spectrum of a light blocking material.

[0099] The terms "green light blocking" or "green light absorbing" refer to the ability of certain particles to absorb, scatter, and / or extinguish incident light in the green region of the visible spectrum (e.g., approximately 500 nm to 578 nm). Thus, the terms "green light blocking" or "green light absorbing" encompass particles that absorb, scatter, and / or extinguish incident light in the green region of the visible spectrum. The particles may be incorporated in various amounts into an optically transparent substrate to achieve an optically transparent material that exhibits a desired level of green light blocking at one or more wavelengths or ranges of wavelengths in the green region.

[0100] As used herein, "nanoparticle (NP)" refers to a particle having at least one dimension that is less than 100 nm. In some cases, a nanoparticle may have at least one dimension that is less than 50 nm. NPs may have a variety of shapes. In some cases, NPs may have a cubic, spherical, rod-shaped, bipyramidal, octahedral, decahedral, cuboctahedral, tetrahedral, rhombic dodecahedral, truncated bisquare prism, or truncated double tetrahedral shape. As used herein, "plasmonic nanoparticle" refers to a metal nanoparticle that has unique optical properties due to localized surface plasmon resonance that allows it to interact with light waves. These properties can be tuned by varying the shape, size, composition, or medium surrounding the surface of the nanoparticle. It will be understood that the term includes all plasmonic nanoparticles of various shapes that will result in surface plasmon absorption and scattering spectra.

[0101] As used herein, a "shape directing agent" is a surfactant or reagent used to grow nanoparticles into a particular morphology. By utilizing a particular shape directing agent, a particular morphology can be selected, thereby allowing the optical properties of the resulting nanoparticles to be tailored. Exemplary shape directing agents include AgNO 3 These agents may include, but are not limited to, CTAB, CTAC, and other such agents known in the art.

[0102] As used herein, "anisotropic" describes a material in which a given property of the material depends on the orientation in which it is measured. Furthermore, something that is "anisotropic" changes size or its physical properties according to the orientation in which it is measured. Examples of anisotropic materials may include graphite, carbon fibers, nanoparticles, etc.

[0103] As used herein, "isotropic" describes a material in which a given property of that material is independent of the orientation in which it is measured. Furthermore, something that is "isotropic" remains constant in size or its physical properties according to the orientation in which it is measured.

[0104] As used herein, "surface energy" may refer to the excess energy (i.e., the difference in energy between a nanoparticle and the same number of atoms in an infinitely extended solid). More broadly, the surface energy of a particle can define its stability given its morphology and is directly related to the thermodynamics of a given nanoparticle.

[0105] As used herein, "surface plasmon resonance (SPR)" refers to the phenomenon in which conduction electrons in a surface layer of a metal can be excited by photons of incident light with a certain angle of incidence, which then causes the excited conduction electrons to propagate parallel to the metal surface in a resonant oscillation (Zeng et al., 2017). For a given light source wavelength and a thin metal surface layer, the certain angle that causes SPR depends on the refractive index of the material near the metal surface. As used herein, "localized surface plasmon resonance (LSPR)" refers to the optical phenomenon generated by light when it interacts with conducting nanoparticles that are smaller than the incident wavelength. As in surface plasmon resonance, the electric field of the incident light can be deposited to collectively excite electrons in the conduction band, and the result is a coherent localized plasmon oscillation with a resonant frequency that is strongly dependent on the NPs' composition, size, geometry, dielectric environment, and separation distance.

[0106] As used herein, "localized surface plasmon resonance (LSPR) peak" refers to the frequency or wavelength of incident light that exhibits the maximum or highest spectral value of localized surface plasmon resonance. With respect to the LSPR peak, two distinct peaks are often observed: a "longitudinal peak" and a "transverse peak." The former is related to the shape of the nanoparticles utilized, while the latter is a result of the intrinsic properties of the material used. For example, gold has an intrinsic transverse peak around 530 nm, but the longitudinal peak of gold NPs can be tuned by adjusting its morphology.

[0107] As used herein, a "plasmonic light blocker" refers to a material that has the ability to absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum due to surface plasmon resonance (SPR) or localized surface plasmon resonance (LSPR), where the wavelength or range of wavelengths blocked corresponds to the wavelength of incident light that induces the SPR or LSPR. Thus, the term "plasmonic light blocker" encompasses particles that absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum due to SPR or LSPR. The particles may be incorporated in various amounts into an optically transparent substrate to achieve an optically transparent material that exhibits a desired level of light filtering at one or more wavelengths or ranges of wavelengths in the electromagnetic spectrum. The percent blocking at a particular wavelength can be determined from the transmission spectrum of the material (blocking percentage=100-percent transmission (%T)).

[0108] As used herein, "tuning" refers to changing the size, shape, surface chemistry, or aggregation state of a nanoparticle to optimize its optical and electronic properties for a particular application. The plasmon peak can be tuned to any wavelength by suitable design of the nanoparticle, as discussed in U.S. Patent No. 9,005,890, which is incorporated herein by reference in its entirety.

[0109] Unless otherwise stated, a numerical range such as, for example, "2 to 10" is inclusive of the numbers defining the range (eg, 2 and 10).

[0110] As used herein, the term "biocompatible" is intended to describe a material that does not elicit a substantial adverse response in vivo. In certain embodiments, a material is "biocompatible" if it is not toxic to cells. In certain embodiments, materials are "biocompatible" if their addition to cells in vitro results in less than 20% cell death, and / or their administration in vivo does not induce inflammation or other such adverse effects.

[0111] As used herein, the term "static concentration" refers to a concentration of a trigger that can vary from about 1% to about 10%. For example, the static concentration can vary by + / - 10%, + / - 5%, + / - 2%, or + / - 1%.

[0112] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0113] Unless otherwise stated, a numerical range such as, for example, "2 to 10" is inclusive of the numbers defining the range (eg, 2 and 10).

[0114] device The resulting optically transparent materials can be used to form a variety of different articles, including optical lenses (e.g., eyeglass lenses, camera lenses, contact lenses, etc.), ophthalmic devices (e.g., contact lenses, corneal onlays, corneal inlays, intraocular lenses, overlay lenses, etc.), screen covers (e.g., transparent sheets configured to cover computer monitors, tablet screens, or cell phone screens), and housings for electronic devices having LED displays. Thus, optical lenses (e.g., eyeglass lenses, camera lenses, contact lenses, etc.), ophthalmic devices (e.g., contact lenses, corneal onlays, corneal inlays, intraocular lenses, overlay lenses, etc.), screen covers (e.g., transparent sheets configured to cover computer monitors, tablet screens, or cell phone screens), and housings for electronic devices having LED displays formed entirely or in part from the optically transparent materials described herein are also provided.

[0115] A variety of ophthalmic devices containing the nanoparticles described herein can be prepared, including hard contact lenses, soft contact lenses, corneal onlays, corneal inlays, intraocular lenses, or overlay lenses. Preferably, the ophthalmic device is a soft contact lens, which can be made from a conventional or silicone hydrogel formulation.

[0116] Ophthalmic devices can be prepared by polymerizing a reactive mixture containing a population of nanoparticles described herein with one or more monomers and optional components suitable for making the desired ophthalmic device. In some cases, the reactive mixture can include, in addition to the population of nanoparticles described above, one or more of a hydrophilic component, a hydrophobic component, a silicone-containing component, a wetting agent such as a polyamide, a crosslinking agent, and additional components such as diluents and initiators.

[0117] Silicone-Containing Components Silicone-containing components suitable for use include one or more polymerizable compounds, each compound independently including at least one polymerizable group, at least one siloxane group, and one or more linking groups connecting the polymerizable group to the siloxane group. The silicone-containing component may contain, for example, 1 to 220 siloxane repeat units, such as those defined below. The silicone-containing component may also contain at least one fluorine atom.

[0118] The silicone-containing component may comprise one or more polymerizable groups as defined above, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units. The silicone-containing component may comprise one or more polymerizable groups that are independently (meth)acrylate, styryl, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, vinyl groups, or mixtures thereof, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0119] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styryl, or mixtures of the foregoing; one or more optionally repeating siloxane units; and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0120] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, or a mixture of the foregoing; one or more optionally repeating siloxane units; and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0121] Formula A. The silicone-containing component may include one or more polymerizable compounds of formula A:

[0122] [ka] During the ceremony, At least one R A is the formula R g -L-, where R g is a polymerizable group, L is a linking group, and the remaining R A are each independently (a)R g -L-, (b) C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 1 ~C 16 Alkyl, (c) C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 3 ~C 12 Cycloalkyl, (d) C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 6 ~C 14 Aryl groups, (e) halo, (f) alkoxy, cyclic alkoxy, or aryloxy, (g) siloxy, (h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl); or (i) a monovalent siloxane chain comprising 1 to 100 siloxane repeat units optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amido, carbamate, halo, or combinations thereof; n is 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20, and when n is other than 0, it is understood that n is a distribution having a mode equivalent to the indicated value. When n is 2 or 3 or more, the SiO units may be the same or different R A may have a substituent, and different R A When substituents are present, the n groups may be in a random or block configuration.

[0123] In formula A, three R A may each contain a polymerizable group, or alternatively two R A may each contain a polymerizable group, or alternatively one R A may contain a polymerizable group.

[0124] Formula B. The silicone-containing component of formula A may be a monofunctional polymerizable compound of formula B:

[0125] [ka] During the ceremony, Rg is a polymerizable group, L is a linking group; j1 and j2 each independently represent an integer of 0 to 220, provided that the sum of j1 and j2 is 1 to 220; R A1 , R A2 , R A3 , R A4 , R A5 , and R A7 independently, in each occurrence, C 1 ~C 6 Alkyl, C 3 ~C 12 Cycloalkyl, C 1 ~C 6 Alkoxy, C 4 ~C 12 cyclic alkoxy, alkoxy-alkyleneoxy-alkyl, aryl (e.g., phenyl), aryl-alkyl (e.g., benzyl), haloalkyl (e.g., partially or fully fluorinated alkyl), siloxy, fluoro, or combinations thereof, wherein each alkyl in the foregoing groups is optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl, each cycloalkyl is optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl, and each aryl is optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl; R A6 is siloxy, C 1 ~C 8 Alkyl (e.g., C 1 ~C 4alkyl, butyl, or methyl), or aryl (eg, phenyl), where the alkyl and aryl may be optionally substituted with one or more fluorine atoms.

[0126] Formula B-1. The compounds of formula B may include compounds of formula B-1, which are compounds of formula B, in which j1 is 0, j2 is 1-220, or j2 is 1-100, or j2 is 1-50, or j2 is 1-20, or j2 is 1-5, or j2 is 1.

[0127] B-2. The compounds of formula B may include compounds of formula B-2, which are compounds of formula B, in which j1 and j2 are independently 4 to 100, or 4 to 20, or 4 to 10, or 24 to 100, or 10 to 100.

[0128] B-3. ​​Compounds of formula B, B-1, and B-2 may include compounds of formula B-3, wherein R A1 , R A2 , R A3 , and R A4 But independently, in each occurrence, C 1 ~C 6 The compounds of formula B, B-1, or B-2 are alkyl or siloxy. Preferred alkyls are 1 ~C 3 Alkyl, or more preferably methyl. A preferred siloxy is trimethylsiloxy.

[0129] B-4. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-4, wherein R A5 and R A7 are independently alkoxy-alkyleneoxy-alkyl, preferably they are independently of the formula CH 3 O-[CH 2 CH 2 O] p -CH 2 CH 2 CH 2wherein p is an integer from 1 to 50, and is a methoxy-capped polyethyleneoxyalkyl of formula B, B-1, B-2, or B-3.

[0130] B-5. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-5, wherein R A5 and R A7 is a compound of formula B, B-1, B-2, or B-3, wherein is independently siloxy, such as trimethylsiloxy.

[0131] B-6. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-6, wherein R A5 and R A7 But independently, C 1 ~C 6 Alkyl, alternatively C 1 ~C 4 alkyl, or alternatively butyl or methyl.

[0132] B-7. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, and B-6 may include compounds of formula B-7, wherein R A6 But, C 1 ~C 8 Alkyl, preferably C 1 ~C 6 Alkyl, more preferably C 1 ~C 4 More preferably, R is an alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl) compound of formula B, B-1, B-2, B-3, B-4, B-5, or B-6. A6 is n-butyl.

[0133] B-8. The compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6 and B-7 may include compounds of formula B-8, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6 or B-7, where Rg includes styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate or (meth)acrylamide. Preferably, Rg includes (meth)acrylate, (meth)acrylamide or styryl. More preferably, Rg includes (meth)acrylate or (meth)acrylamide.

[0134] When Rg is (meth)acrylamide, the nitrogen group is R A9 and R A9 , H, C 1 ~C 8 Alkyl (preferably C 1 ~C 4 alkyl, e.g., n-butyl, n-propyl, methyl, or ethyl), or C 3 ~C 8 Cycloalkyl (preferably C 5 ~C 6 cycloalkyl), where the alkyl and cycloalkyl are optionally substituted with one or more groups independently selected from hydroxyl, amide, ether, silyl (e.g., trimethylsilyl), siloxy (e.g., trimethylsiloxy), alkyl-siloxanyl (wherein the alkyl is itself optionally substituted with fluoro), aryl-siloxanyl (wherein the aryl is itself optionally substituted with fluoro), and silyl-oxaalkylene (wherein the oxaalkylene is itself optionally substituted with hydroxyl).

[0135] B-9. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, and B-8 may include compounds of formula B-9, in which the linking group is an alkylene (preferably C 1 ~C 4 alkylene), cycloalkylene (preferably C 5 ~C6 Cycloalkylene), alkyleneoxy (preferably ethyleneoxy), haloalkyleneoxy (preferably haloethyleneoxy), amide, oxaalkylene (preferably containing 3 to 6 carbon atoms), siloxanyl, alkylenesiloxanyl, carbamate, alkyleneamine (preferably C 1 ~C 6 alkyleneamine), or a combination of two or more thereof, wherein the linking groups are optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, siloxy, and carbamate.

[0136] B-10. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-10, in which the linking group is alkylene-siloxanyl-alkylene-alkyleneoxy- or alkylene-siloxanyl-alkylene-[alkyleneoxy-alkylene-siloxanyl] q -alkyleneoxy- (wherein q is 1 to 50).

[0137] B-11. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-11, wherein the linking group is 1 ~C 6 Alkylene, preferably C 1 ~C 3 The compound of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 is an alkylene, more preferably n-propylene.

[0138] B-12. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-12, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, in which the linking group is alkylene-carbamate-oxaalkylene. Preferably, the linking group is CH 2 CH 2 N(H)-C(=O)-O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 It is.

[0139] B-13. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-13, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, in which the linking group is oxaalkylene. Preferably, the linking group is CH 2 CH 2 -O-CH 2 CH 2 CH 2 It is.

[0140] B-14. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-14, wherein the linking group is alkylene-[siloxanyl-alkylene] q -, where q is 1 to 50. Examples of such linking groups are -(CH 2 ) 3 -[Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -(CH 2 ) 2 ] q -It is.

[0141] B-15. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-15, in which the linking group is alkyleneoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene, and the cycloalkylene is selected from one, two, or three independently selected alkyl groups (preferably C 1 ~C 3 and m is 0, 1 or 2. Examples of such linking groups are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, optionally substituted with -[OCH 2 CH 2 ] q -OC(=O)-NH-CH 2 -[1,3-Cyclohexylene]-NHC(=O)O-CH 2 CH 2 -O-CH 2 CH 2 - in which the cyclohexylene is substituted with three methyl groups at the 1 and 5 positions.

[0142] B-16. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-16, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is alkyleneoxy, where each alkylene in the alkyleneoxy is independently optionally substituted with hydroxyl. Examples of such linking groups include -O-(CH 2 ) 3 Another example of such a linking group is -O-CH 2 CH(OH)CH 2 -O-(CH 2 ) 3 -It is.

[0143] B-17. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-17, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is an alkyleneamine. Examples of such linking groups include -NH-(CH 2 ) 3 -It is.

[0144] B-18. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-18, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, in which the linking group is an oxaalkylene optionally substituted with hydroxyl, siloxy, or silyl-alkyleneoxy (alkyleneoxy itself optionally substituted with hydroxyl). Examples of such linking groups are -CH 2 CH(G)CH 2 -O-(CH 2 ) 3 -, where G is hydroxyl. In another example, G is R 3 SiO-, two R groups are trimethylsiloxy and the third is C 1 ~C 8 Alkyl (preferably C 1 ~C 3 alkyl, more preferably methyl) or the third is C 3 ~C 8 In a further example, G is R 3 Si-(CH 2 ) 3 -O-CH 2 CH(OH)CH 2 -O-, two R groups are trimethylsiloxy and the third is C 1 ~C 8 Alkyl (preferably C 1 ~C 3 alkyl, more preferably methyl) or C 3 ~C 8In yet a further example, G is a polymerizable group, such as (meth)acrylate. Such compounds can function as crosslinkers.

[0145] B-19. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-19, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is an amine-oxaalkylene optionally substituted with hydroxyl. Another example of such a linking group is -NH-CH 2 CH(OH)CH 2 -O-(CH 2 ) 3 -It is.

[0146] B-20. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-20, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is alkyleneoxy-carbamate-oxaalkylene. Examples of such linking groups include -O-(CH 2 ) 2 -N(H)C(=O)O-(CH 2 ) 2 -O-(CH 2 ) 3 -It is.

[0147] B-21. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-21, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, in which the linking group is alkylene-carbamate-oxaalkylene. Examples of such linking groups include -(CH 2 ) 2 -N(H)C(=O)O-(CH 2 ) 2 -O-(CH2 ) 3 -It is.

[0148] The silicone-containing components of formula C. A, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, and B-21 may include compounds of formula C, which are compounds of formula A, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, or B-21 having the following structure:

[0149] [ka] During the ceremony, R A8 is hydrogen or methyl, Z is O, S, or N(R A9 ) and L, j1, j2, R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A9 is as defined in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0150] C-1. Compounds of formula C may include (meth)acrylates of formula C-1, which are compounds of formula C where Z is O.

[0151] C-2. Compounds of formula C may include (meth)acrylamides of formula C-2, where Z is N(R A9 ) and R A9 is H.

[0152] C-3. Compounds of formula C may include (meth)acrylamides of formula C-3, where Z is N(R A9) and R A9 is unsubstituted or optionally substituted as above; 1 ~C 8 R is a compound of formula C, A9 Examples of 3 , -CH 2 CH(OH)CH 2 (OH), -(CH 2 ) 3 -Siloxanyl, -(CH 2 ) 3 -SiR 3 , and -CH 2 CH(OH)CH 2 -O-(CH 2 ) 3 -SiR 3 Each R in the above groups is trimethylsiloxy, C 1 ~C 8 Alkyl (preferably C 1 ~C 3 alkyl, more preferably methyl), and C 3 ~C 8 cycloalkyl. R A9 Further examples of the group include -(CH 2 ) 3 -Si(Me)(SiMe 3 ) 2 , and -(CH 2 ) 3 -Si(Me 2 )-[O-SiMe 2 ] 1-10 -CH 3 Examples include:

[0153] Formula D. Compounds of formula C may include compounds of formula D:

[0154] [ka] During the ceremony, R A8 is hydrogen or methyl, Z 1 is O or N(R A9 ) and L1 is an alkylene containing 1 to 8 carbon atoms or an oxaalkylene containing 3 to 10 carbon atoms; L 1 is optionally substituted with hydroxyl; j2, R A3 , R A4 , R A5 , R A6 , R A7 , and R A9 is as defined above in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0155] D-1. Compounds of formula D may include compounds of formula D-1, wherein L 1 is optionally substituted with hydroxyl 2 ~C 5 Preferably, L is a compound of formula D, 1 is n-propylene optionally substituted with hydroxyl.

[0156] D-2. Compounds of formula D may include compounds of formula D-2, wherein L 1 is an oxaalkylene containing 4 to 8 carbon atoms optionally substituted with hydroxyl. 1 is an oxaalkylene containing 5 or 6 carbon atoms optionally substituted with hydroxyl. Examples include -(CH 2 ) 2 -O-(CH 2 ) 3 - and -CH 2 CH(OH)CH 2 -O-(CH 2 ) 3 -- are some examples.

[0157] D-3. Compounds of formula D, D-1, and D-2 may include compounds of formula D-3, wherein Z 1 is O.

[0158] D-4. Compounds of formula D, D-1, and D-2 may include compounds of formula D-4, wherein Z 1 N(R A9 ) and R A9 is H.

[0159] D-5. Compounds of formula D, D-1, and D-2 may include compounds of formula D-5, wherein Z 1 N(R A9 ) and R A9 Hydroxyl, siloxy, and C 1 ~C 6 C optionally substituted with one or two substituents selected from alkyl-siloxanyl- 1 ~C 4 The compound is of formula D, D-1, or D-2, wherein R is an alkyl group.

[0160] D-6. Compounds of formula D, D-1, D-2, D-3, D-4, and D-5 may include compounds of formula D-6, which are compounds of formula D, D-1, D-2, D-3, D-4, or D-5, where j2 is 1.

[0161] D-7. Compounds of formula D, D-1, D-2, D-3, D-4, and D-5 may include compounds of formula D-7, which are compounds of formula D, D-1, D-2, D-3, D-4, or D-5, wherein j2 is 2 to 220, or 2 to 100, or 10 to 100, or 24 to 100, or 4 to 20, or 4 to 10.

[0162] D-8. Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 may include compounds of formula D-8, wherein R A3 , R A4 , R A5 , R A6 , and R A7 But independently, C 1 ~C 6 The compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, or D-7 are preferably alkyl or siloxy.A3 , R A4 , R A5 , R A6 , and R A7 is independently selected from methyl, ethyl, n-propyl, n-butyl, and trimethylsiloxy. More preferably, R A3 , R A4 , R A5 , R A6 , and R A7 is independently selected from methyl, n-butyl, and trimethylsiloxy.

[0163] D-9. Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 may include compounds of formula D-9, wherein R A3 and R A4 But independently, C 1 ~C 6 alkyl (e.g., methyl or ethyl) or siloxy (e.g., trimethylsiloxy), R A5 , R A6 , and R A7 But independently, C 1 ~C 6 The compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, or D-7, wherein R is alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).

[0164] The silicone-containing component of formula E may include a multifunctional silicone-containing component. Thus, for example, the silicone-containing component of formula A may include a difunctional material of formula E:

[0165] [ka] During the ceremony, Rg, L, j1, j2, R A1 , R A2 , R A3 , R A4 , R A5 , and R A7 is as defined above for formula B or its various subformulas (e.g., B-1, B-2, etc.); L 2 is a linking group, Rg 1 is a polymerizable group.

[0166] E-1. Compounds of formula E may include compounds of formula E-1, wherein Rg and Rg 1 are the structures CH 2 =CH-OC(=O)-O- or structure CH 2 =C(CH 3 )-OC(=O)-O-, a compound of formula E.

[0167] E-2. Compounds of formula E may include compounds of formula E-2, wherein Rg and Rg 1 are each (meth)acrylates.

[0168] E-3. Compounds of formula E may include compounds of formula E-3, wherein Rg and Rg 1 are (meth)acrylamides, and the nitrogen group is R A9 (R A9 is as defined above), a compound of formula E.

[0169] E-4. Suitable compounds of formula E, E-1, E-2, and E-3 include compounds of formula E-4, which are compounds of formula E, E-1, E-2, or E-3, wherein j1 is 0 and j2 is 1 to 220, or j2 is 1 to 100, or j2 is 1 to 50, or j2 is 1 to 20.

[0170] E-5. Suitable compounds of formulas E, E-1, E-2, and E-3 include compounds of formula E-5, which are compounds of formulas E, E-1, E-2, or E-3, wherein j1 and j2 are independently 4 to 100.

[0171] E-6. Suitable compounds of formula E, E-1, E-2, E-3, E-4, and E-5 include compounds of formula E-6, wherein R A1, R A2 , R A3 , R A4 , and R A5 But independently, in each occurrence, C 1 ~C 6 alkyl or preferably they are independently C 1 ~C 3 and preferably, each of the compounds of formula E, E-1, E-2, E-3, E-4, or E-5 is alkyl or methyl.

[0172] E-7. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, and E-6 include compounds of formula E-7, wherein R A7 is an alkoxy-alkyleneoxy-alkyl, preferably of the formula CH 3 O-[CH 2 CH 2 O] p -CH 2 CH 2 CH 2 (wherein p is an integer from 1 to 50, or 1 to 30, or 1 to 10, or 6 to 10),

[0173] E-8. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, and E-7 include compounds of formula E-8, which are compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, or E-7, where L comprises alkylene, carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, or a combination of two or more thereof, and the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

[0174] E-9. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, E-7, and E-8 include compounds of formula E-9, wherein L2 comprises an alkylene, carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, or a combination of two or more thereof, and the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

[0175] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in the table below. When a compound in the table below contains a polysiloxane group, the number of Si repeat units in such a compound is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0176] [Table 1-1]

[0177] [Table 1-2]

[0178] Additional non-limiting examples of suitable silicone-containing components are listed in the table below. Unless otherwise stated, where applicable, j2 is preferably 1 to 100, more preferably 3 to 40, or even more preferably 3 to 15. In compounds containing j1 and j2, the sum of j1 and j2 is preferably 2 to 100, more preferably 3 to 40, or even more preferably 3 to 15.

[0179] [Table 2-1]

[0180] [Table 2-2]

[0181] The silicone-containing component can have an average molecular weight of about 400 to about 4000 Daltons.

[0182] The silicone-containing component may be present in an amount up to about 95%, or from about 10 to about 80%, or from about 20 to about 70% by weight of the reactive mixture (excluding the diluent), based on all reactive components.

[0183] polyamide The reactive monomer mixture may include at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers that include repeat units that contain amide groups. The polyamide may include cyclic amide groups, non-cyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Non-cyclic polyamides include pendant non-cyclic amide groups and are capable of association with hydroxyl groups. Cyclic polyamides include cyclic amide groups and are capable of association with hydroxyl groups.

[0184] Examples of suitable acyclic polyamides include polymers and copolymers comprising repeat units of formulae G1 and G2,

[0185] [ka] In the formula, X is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is C 1 ~C 3 is an alkyl group, R 40 is H, straight or branched chain, substituted or unsubstituted C 1 ~C 4 alkyl groups; R 41 is H, straight or branched chain, substituted or unsubstituted C 1 ~C 4R is selected from an alkyl group, an amino group having up to 2 carbon atoms, an amide group having up to 4 carbon atoms, and an alkoxy group having up to 2 carbon atoms; 42 is H, straight or branched chain, substituted or unsubstituted C 1 ~C 4 alkyl groups or selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 43 is H, straight or branched chain, substituted or unsubstituted C 1 ~C 4 alkyl groups or selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 40 and R 41 The number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or fewer, in total; 42 and R 43 The number of carbon atoms in R is 8 or less in total, including 7, 6, 5, 4, 3, or fewer. 40 and R 41 The total number of carbon atoms in R may be 6 or less, or 4 or less. 42 and R 43 The total number of carbon atoms in the alkyl group may be up to 6. As used herein, a substituted alkyl group includes an alkyl group substituted with an amine group, an amide group, an ether group, a hydroxyl group, a carbonyl group, or a carboxyl group, or a combination thereof.

[0186] R 40 and R 41 is H, substituted or unsubstituted C 1 ~C 2 X may be a direct bond, R 40 and R 41 is H, substituted or unsubstituted C 1 ~C 2 R may be independently selected from alkyl groups. 42 and R 43 is H, substituted or unsubstituted C 1 ~C 2 The alkyl groups may be independently selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0187] The acyclic polyamide of the present invention may contain the repeating unit of formula LV or formula LVI as a main part, or the acyclic polyamide may contain at least 50 mol% of the repeating unit of formula G or formula G1, such as at least about 70 mol% and at least 80 mol%. Specific examples of the repeating units of formula G and formula G1 include N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, N-vinyl-2-methyl-propionamide, N-vinyl-N,N'-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and repeating units derived from acrylamides of formula G2 and G3.

[0188]

Chemical formula

[0189] Examples of suitable cyclic amides that can be used to form cyclic polyamides include α-lactam, β-lactam, γ-lactam, δ-lactam, and ε-lactam. Examples of suitable cyclic polyamides include polymers and copolymers containing the repeating unit of formula G4,

[0190]

Chemical formula

[0191] The cyclic polyamide may comprise 50 mole percent or more of repeat units of formula G4, or the cyclic polyamide may comprise at least 50 mole percent of repeat units of formula G4, such as at least 70 mole percent, and at least 80 mole percent.

[0192] Polyamides may also be copolymers containing both cyclic and non-cyclic amide repeat units. The additional repeat units may be formed from monomers selected from hydroxyalkyl (meth)acrylates, alkyl (meth)acrylates, other hydrophilic monomers, and siloxane-substituted (meth)acrylates. Any of the monomers listed as suitable hydrophilic monomers may be used as comonomers to form the additional repeat units. Specific examples of additional monomers that may be used to form polyamides include 2-hydroxyethyl (meth)acrylate, vinyl acetate, acrylonitrile, hydroxypropyl (meth)acrylate, methyl (meth)acrylate and hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like, and mixtures thereof. Ionic monomers may also be included. Examples of ionic monomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine (VINAL, CAS#148969-96-4), 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid (AMBA), 2-(methacryloyloxy)ethyl trimethylammonium chloride (Q salt or 2-(methacryloyloxy)ethyl trimethylammonium chloride, METAC), 2-acrylamido-2-methylpropane sulfonic acid, acid, AMPS), 1-propanaminium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, inner salt (CBT), 1-propanaminium, N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt (SBT), 3,5-Dioxa-8-aza-4-phosphane-10-en-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT), 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate Examples of such compounds include 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS), and 3-((3-(methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

[0193] The reactive monomer mixture may include both acyclic and cyclic polyamides or copolymers thereof. The acyclic polyamide may be any of the acyclic polyamides or copolymers thereof described herein, while the cyclic polyamide may be any of the cyclic polyamides or copolymers thereof described herein. The polyamide may be selected from the group of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof.

[0194] The total amount of all polyamides in the reactive mixture can range from 1 weight percent to about 35 weight percent, such as from 1 weight percent to about 15 weight percent, and from about 5 weight percent to about 15 weight percent, in all cases based on the total weight of the reactive components of the reactive monomer mixture.

[0195] Without being bound by theory, when used with silicone hydrogels, polyamides function as internal wetting agents. The polyamides may be non-polymeric, in which case they are incorporated into the silicone hydrogel as a semi-interpenetrating network. The polyamides are encapsulated or physically held within the silicone hydrogel. Alternatively, the polyamides may be polymeric, for example as polyamide macromers or prepolymers, in which case they are covalently incorporated into the silicone hydrogel. Mixtures of polymeric and non-polymeric polyamides may also be used.

[0196] When a polyamide is incorporated within the reactive monomer mixture, the polyamide may have a weight average molecular weight of at least 100,000 Daltons, greater than about 150,000, from about 150,000 to about 2,000,000 Daltons, from about 300,000 Daltons to about 1,800,000 Daltons. Higher molecular weight polyamides may be used if compatible with the reactive monomer mixture.

[0197] When the compositions described herein are used in silicone hydrogel contact lenses, the lenses may preferably exhibit the following characteristics. All values ​​are preceded by "about", and the lenses may have any combination of the listed characteristics. The characteristics can be determined by methods known to those skilled in the art, for example, as described in U.S. Patent Application Publication No. 20180037690, which is incorporated herein by reference.

[0198] Water content by weight: at least 20%, at least 25%, at least about 30%, or at least about 35%, and up to 80% or up to 70% Haze: 30% or less, or 10% or less Advancing dynamic contact angle (Wilhelmy plate method): 100° or less, 80° or less, or 50° or less Tensile modulus (psi): 120 or less, or 80-120 Oxygen permeability (Dk, Barrer): at least 80, or at least 100, or at least 150, or at least 200 Elongation at break: at least 100 With respect to ionic silicone hydrogels, the following properties (in addition to those mentioned above) may also be preferred: Lysozyme uptake (μg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 or less EXAMPLES

[0199] The present disclosure includes at least the following examples, which are intended to further illustrate certain aspects of the materials and methods described herein, and are not intended to limit the scope of the claims.

[0200] Aspect 1: A composition for light filtering, the composition comprising: a base material; a plurality of gold nanoparticles dispersed in the base material, the plurality of gold nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm and having a full width at half maximum (FWHM) of about 30 nm to about 100 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derivatized monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

[0201] Embodiment 2: The composition of embodiment 1, wherein the base material comprises a biomaterial.

[0202] Embodiment 3: The composition of embodiment 1, wherein the base material comprises a biomaterial matrix.

[0203] Embodiment 4: The composition of embodiment 1, wherein the base material comprises a hydrogel.

[0204] Embodiment 5: The composition of embodiment 1, wherein the base material comprises a silicone-based hydrogel.

[0205] Example 6. The composition of example 1, wherein the base material comprises a HEMA-based material.

[0206] Embodiment 7: The composition of any one of embodiments 1-6, wherein at least a portion of the plurality of gold nanoparticles comprises a sphere, a rod, a bipyramid, or a star shape.

[0207] Aspect 8: The composition of any one of aspects 1-7, wherein one or more of the sizes or shapes of at least a portion of the plurality of gold nanoparticles are adjusted such that a portion of the plurality of gold nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm.

[0208] Embodiment 9: The composition of any one of embodiments 1 to 8, wherein at least a portion of the plurality of gold nanoparticles comprises a size of about 1 nm to about 99 nm.

[0209] Embodiment 10: The composition of any one of embodiments 1 to 9, wherein the fixing mechanism comprises glycidyl methacrylate.

[0210] Example 11: The composition of any one of Examples 1 to 10, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

[0211] Aspect 12: A composition for light filtering, the composition comprising: a base material comprising a HEMA-based material; a plurality of metallic nanoparticles dispersed in the base material, the plurality of metallic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of metallic nanoparticles.

[0212] Example 13: The composition of example 12, wherein at least a portion of the plurality of metal nanoparticles comprises a sphere, a rod, a bipyramid, or a star shape.

[0213] Example 14: The composition of any one of Examples 12-13, wherein at least a portion of the plurality of metal nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm.

[0214] Aspect 15: The composition of any one of aspects 12-14, wherein one or more of the sizes or shapes of at least a portion of the plurality of metal nanoparticles are tailored such that a portion of the plurality of metal nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm.

[0215] Example 16: The composition of any one of Examples 12-15, wherein at least a portion of the plurality of metal nanoparticles comprises a size of from about 1 nm to about 99 nm.

[0216] Embodiment 17: The composition of any one of embodiments 12-16, wherein the fixing mechanism comprises glycidyl methacrylate.

[0217] Embodiment 18: The composition of any one of embodiments 12 to 17, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

[0218] Embodiment 19: A composition for light filtering, the composition comprising: a base material comprising a HEMA-based material; a plurality of plasmonic nanoparticles dispersed in the base material, the plurality of plasmonic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of plasmonic nanoparticles.

[0219] Example 20: The composition of example 19, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a spherical shape, a rod shape, a bipyramidal shape, a star shape, a decahedral shape, a cuboctahedral shape, or a cube shape.

[0220] Example 21: The composition of any one of Examples 19-20, wherein at least a portion of the plurality of plasmonic nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm.

[0221] Example 22: The composition of any one of Examples 19-21, wherein one or more of the sizes or shapes of at least a portion of the plurality of plasmonic nanoparticles are tailored such that a portion of the plurality of plasmonic nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm.

[0222] Example 23: The composition of any one of Examples 19 to 22, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a size between about 1 nm and about 99 nm.

[0223] Embodiment 24: The composition of any one of embodiments 19 to 23, wherein the fixing mechanism comprises glycidyl methacrylate.

[0224] Embodiment 25: The composition of any one of embodiments 19 to 24, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

[0225] As an illustrative example, Figures 1-4 show how light filtering in the region between red and green cones can help improve contrast and color perception for people with red-green color vision deficiency (Figure 1). A platform was developed using gold nanoparticles to selectively block light in a target range. The platform leverages the localized surface plasmon resonance (LSPR) peak of spherical gold nanoparticles (AuNPs) to adapt the light filtering profile.

[0226] FIG. 1 is a schematic diagram of an example surface modification strategy. FIG. 1 illustrates a method to artificially block the area between red and green cones to improve contrast in people with red-green color vision deficiency. The most significant obstacle that had to be overcome in devising the surface modification strategy was maintaining the colloidal stability of methacrylated polyvinyl alcohol-nanospheres (PVA-NS) in water. Methacrylation increased the hydrophobicity of the NS surface, making NS more likely to aggregate in polar solvents such as water. Polyvinyl alcohol-nanoparticles (PVA-NPs) of increasing PVA molecular weight (10 kDa, 80% hydrolyzed; 20 kDa and 40 kDa, both >98% hydrolyzed) were methacrylated in dimethylsulfoxide (DMSO) with 3.77 μl of glycidyl methacrylate (GMA) and centrifuged at 12,000×g for 15 min. After resuspension in MilliQ water and centrifugation, all samples were aggregated. Dark spots and tails were observed at the bottom of each tube of aggregated NPs, indicating that resuspension of the NPs by sonication was not successful (Figure 3).

[0227] Attempts were devised to mitigate aggregation using surfactants, which are amphiphilic and could potentially help to passivate the surface of the PVA-NS to prevent aggregation. One parameter that was investigated was the hydrophilic-lipophilic balance (HLB), a common tool used to assess the relative solubility of a given surfactant in water versus oil. HLB is a scale from 0 (fully hydrophobic) to 18 (fully hydrophilic) (Hakemi-Vala, M., et al., Nano-Microscale Drug Deliv. Syst. Des. Fabr (2017)). Matching the HLB of the surfactants with that of the emulsions minimizes interfacial tension, improves their stability, and reduces flocculation. Although the PVA-NS solutions were not emulsions, it was thought that this phenomenon could be used for methacrylated PVA-NS to produce similar results and improve aqueous stability. Two common surfactants, cetyltrimethylammonium bromide (CTAB, 4 mM, HLB: 10) and Tween 20 (4 mM, HLB: 17), were used to generate surfactant mixtures with effective HLB values ​​of 10, 11.75, 13.5, 15.25, and 17 and tested for their effect on nanoparticle stability after centrifugation (Figure 4). No significant differences were observed between the HLB values: all samples aggregated in water after centrifugation.

[0228] Because the effectiveness of surfactants in stabilizing NPs in solution may depend on interactions with the NS surface (including interactions with PVA and methacrylate groups) or other factors other than HLB value, the selection of surfactants was expanded to include Tetronic (24 mM, HLB 15) and Pluronic F-127 (90 mM, HLB 18-24) in an attempt to further improve stability. Pluronic F-127 improved recovery after centrifugation of methacrylated PVA-NS the most, but required high concentrations (>200 mM) to achieve acceptable recovery after centrifugation. Although sufficient improvement was not seen by changing the surfactant, other factors were considered.

[0229] To increase hydrophilicity and stabilize the PVA-NS, small amounts of 55 kDa PVP were added to the PVA-NS surface (1 mM or 0.1114 mg / ml PVP compared to 4 mM or 2 mg / ml PVA). In addition to using the surfactant Pluronic F-127 (90 mM), this system was tested to determine whether PVA-NS could be stabilized with different degrees of methacrylation (Figure 5).

[0230] PVA-NS were methacrylated with increasing amounts of glycidyl methacrylate (GMA) and resuspended in either MilliQ water or a solution of 90 mM Pluronic F-127 after methacrylation according to Table 1 below. All PVA-NS showed some discoloration and aggregation after methacrylation, but the inclusion of lower amounts of GMA and Pluronic F-127 in combination improved recovery.

[0231] [Table 3]

[0232] Samples a and b from Table 1 were incorporated into contact lenses to determine whether color and stability could be sustained in an etafilcon A lens matrix (FIGS. 6A-6B). Both samples a and b produced colored lenses (FIG. 5A) (consistent with the UV-Vis spectra shown in FIG. 6B) and demonstrated improved recovery in the presence of PVP. Compared to the stability afforded by PVP, the presence of Pluronic F-127 in the suspension did not significantly improve the stability of methacrylated PVA-NS.

[0233] Considering the above, the surface chemistry of gold nanoparticles (AuNPs) was designed to be chemically and physically lens compatible and to be capable of covalent integration with the monomer mixture. In the case of etafilcon lenses, the main monomer was 2-hydroxyethyl methacrylate (HEMA), a methacrylate compound with a double bond carbon for radical polymerization. Thus, as can be seen in Figure 2, AuNPs were coated with poly(vinyl alcohol) (PVA) and methacrylated with glycidyl methacrylate using transesterification. In a 20 ml scintillation vial, 45 mM PVA (10 kDa, 8 ml) and nanospheres (NS) (8 ml) were combined to produce PVA-NS. A small amount of 55 kDa polyvinylpyrrolidone PVP (approximately 2 mol% compared to PVA) was added to improve the stability and hydrophilicity of PVA-NS. The samples were left overnight in a fume hood and used the next day. PVA-NS was centrifuged twice at 12,000×g for 15 min and resuspended in 5 ml of dimethyl sulfoxide (DMSO). In a 20 ml scintillation vial, PVA-NS (5 ml), glycidyl methacrylate (GMA) (0.94 μl), and tetramethylethylenediamine (TEMED) (3.39 μl) were added sequentially and stirred at 1000 rpm for 6 h at 60°C. Aluminum foil was used to protect the vial from light to avoid polymerization of GMA. After the reaction was completed, the methacrylated PVA-NS was centrifuged twice at 12,000×g for 15 min and resuspended in 5 ml and 0.25 ml of MilliQ water, respectively, via sonication.

[0234] All infrared (IR) measurements were performed using a Nicolet iS50 Fourier transform infrared (FTIR) equipped with an attenuated total reflection (ATR) accessory from Thermo Scientific. Data were collected with OMNIC software. The wavelength range collected was 4000–400 cm. -1 (Process size: 0.17cm -1) with 16 scans per sample. FTIR spectra were compared to the literature to identify peaks.

[0235] Methacrylated AuNPs retained colloidal stability with a slight blue-shift shift in their light filtering spectra, as can be seen in Figures 7A-7B, showing the effect of methacrylation on light filtering spectra in solution. PVAs of different molecular weights and degrees of hydrolysis were chosen. Nanoparticles were coated with 20 kDa (Figure 7A) or 40 kDa (Figure 7B) PVA and either methacrylated or not. Methacrylated AuNPs were then mixed with etafilcon monomer mixture and cured under blue light to produce contact lenses. Ultraviolet-visible (UV-Vis) spectra show that the LSPR was maintained in the contact lenses for all samples, as can be seen in the graph in Figure 8A. The image in Figure 8B shows that the AuNPs were uniformly dispersed within the lenses with a consistent profile along the entire material. The peaks were red-shifted compared to the suspension in solution and were nearly identical to the original spectrum before methacrylation.

[0236] The materials of the present disclosure were autoclave stable, as is important for commercialization of contact lenses. NP retention was determined by measuring the level of Au leaching from the lenses after autoclaving, as shown in FIG. 9. FIG. 9 further illustrates sample preparation for ICP-MS measurements. The resulting lenses had less than about 100 ppb (0.1 ppm) Au in solution, translating to less than about 1 μg total Au released per lens, as can be seen in Table 1 below. FIG. 1B illustrates an example of methacrylation of PVA through a reaction pathway (adapted from Crispim, et al., e-Polymers, 2006), and the Fourier transform infrared (FTIR) spectrum (FIG. 2) of poly(vinyl alcohol) (PVA) conjugated with glycidyl methacrylate (GMA).

[0237] Table 1 below shows the Au leaching from contact lenses. Contact lenses containing NPs were autoclaved and evaluated for Au leaching to determine retention of Au nanoparticles.

[0238] [Table 4]

[0239] The systems, methods, compositions, and devices of the appended claims are not limited in scope by the specific materials and devices described herein, but are intended as examples of some aspects of the claims. Any systems, methods, compositions, and devices that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the systems, methods, compositions, and devices in addition to those shown and described herein are intended to fall within the scope of the appended claims. Furthermore, although only certain representative systems, methods, compositions, and devices disclosed herein are specifically described, other combinations of systems, methods, compositions, and devices are also intended to fall within the scope of the appended claims, even if not specifically described. Thus, although elements, components, or combinations of components may be explicitly referred to herein, other combinations of elements, components, and components are included even if not explicitly described.

[0240] As used herein, the term "comprising" and variations thereof are open, non-limiting terms used synonymously with the term "including" and variations thereof. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention and are disclosed. Unless otherwise specified, all numbers expressing geometric shapes, dimensions, and the like used in the specification and claims should be understood to be interpreted in light of the number of significant digits and ordinary rounding techniques, at least without intending to limit the application of the doctrine of equivalents to the scope of the claims.

[0241] 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 to which the disclosed invention belongs. Publications cited herein and the material for which they are cited are specifically incorporated by reference.

[0242] [Embodiment] (1) A composition for light filtering, said composition comprising: A base material; a plurality of gold nanoparticles dispersed in the base material, the plurality of gold nanoparticles exhibiting a peak optical absorption value in the range of about 500 nm to about 600 nm and having a full width at half maximum (FWHM) of about 30 nm to about 100 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles. (2) The composition of embodiment 1, wherein the base material comprises a biomaterial. (3) The composition of embodiment 1, wherein the base material comprises a biomaterial matrix. (4) The composition of embodiment 1, wherein the base material comprises a hydrogel. (5) The composition of claim 1, wherein the base material comprises a silicone-based hydrogel.

[0243] (6) The composition of embodiment 1, wherein the base material comprises a HEMA-based material. (7) The composition of embodiment 1, wherein at least a portion of the plurality of gold nanoparticles comprises a sphere, a rod, a bipyramid, or a star shape. (8) The composition of embodiment 1, wherein one or more of the sizes or shapes of at least a portion of the plurality of gold nanoparticles are adjusted such that said portion of the plurality of gold nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm. (9) The composition of embodiment 1, wherein at least a portion of the plurality of gold nanoparticles comprises a size of about 1 nm to about 99 nm. (10) The composition of embodiment 1, wherein the fixing mechanism comprises glycidyl methacrylate.

[0244] (11) The composition of claim 1, wherein the nanoparticle coating material comprises poly(vinyl alcohol). (12) A composition for light filtering, said composition comprising: a base material comprising a HEMA-based material; a plurality of metal nanoparticles dispersed in the base material, the plurality of metal nanoparticles exhibiting a peak optical absorption value in the range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; a nanoparticle coating material disposed on at least a portion of the plurality of metal nanoparticles. 13. The composition of claim 12, wherein at least a portion of the plurality of metal nanoparticles comprises a sphere, a rod, a bipyramid, or a star shape. (14) The composition of embodiment 12, wherein at least a portion of the plurality of metal nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm. (15) The composition of embodiment 12, wherein one or more of the sizes or shapes of at least a portion of the plurality of metal nanoparticles are adjusted such that the portion of the plurality of metal nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm.

[0245] 16. The composition of claim 12, wherein at least a portion of the plurality of metal nanoparticles comprises a size of about 1 nm to about 99 nm. 17. The composition of claim 12, wherein the fixing mechanism comprises glycidyl methacrylate. 18. The composition of claim 12, wherein the nanoparticle coating material comprises poly(vinyl alcohol). (19) A composition for light filtering, said composition comprising: a base material comprising a HEMA-based material; a plurality of plasmonic nanoparticles dispersed in the base material, the plurality of plasmonic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; a nanoparticle coating material disposed on at least a portion of the plurality of plasmonic nanoparticles. (20) The composition of embodiment 19, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a spherical shape, a rod shape, a bipyramidal shape, a star shape, a decahedral shape, a cuboctahedral shape, or a cube shape.

[0246] (21) The composition of embodiment 19, wherein at least a portion of the plurality of plasmonic nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm. (22) The composition of embodiment 19, wherein one or more of the sizes or shapes of at least a portion of the plurality of plasmonic nanoparticles are tailored such that the portion of the plurality of plasmonic nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm. (23) The composition of embodiment 19, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a size of about 1 nm to about 99 nm. 24. The composition of claim 19, wherein the fixing mechanism comprises glycidyl methacrylate. 25. The composition of claim 19, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

[0247] (26) A contact lens comprising a composition for light filtering, said composition exhibiting a peak light absorption value in the range of about 500 nm to about 600 nm, said peak having a full width at half maximum (FWHM) of about 30 nm to about 100 nm, said contact lens comprising a HEMA-based material. (27) The contact lens of embodiment 26, wherein the composition comprises a plurality of plasmonic nanoparticles and an anchoring mechanism dispersed throughout the contact lens, the anchoring mechanism comprising a methacryloyl-derivatized monomer, and a nanoparticle coating material disposed on at least a portion of the plurality of plasmonic nanoparticles. (28) The contact lens of embodiment 27, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a spherical shape, a rod shape, a bipyramidal shape, a star shape, a decahedral shape, a cuboctahedral shape, or a cube shape. (29) The contact lens of embodiment 27, wherein one or more of the sizes or shapes of at least a portion of the plurality of plasmonic nanoparticles are tailored such that the portion of the plurality of plasmonic nanoparticles exhibits a peak optical absorption in the range of about 500 nm to about 600 nm. (30) The contact lens of embodiment 27, wherein at least a portion of the plurality of plasmonic nanoparticles have a size ranging from about 1 nm to about 99 nm.

[0248] (31) The contact lens of embodiment 27, wherein the fixation mechanism comprises glycidyl methacrylate. (32) The contact lens of embodiment 27, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

Claims

1. A composition for light filtering, said composition comprising: A base material; a plurality of gold nanoparticles dispersed in the base material, the plurality of gold nanoparticles exhibiting a peak optical absorption value in the range of about 500 nm to about 600 nm and having a full width at half maximum (FWHM) of about 30 nm to about 100 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

2. A composition for light filtering, said composition comprising: a base material comprising a HEMA-based material; a plurality of metal nanoparticles dispersed in the base material, the plurality of metal nanoparticles exhibiting a peak optical absorption value in the range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of metal nanoparticles.

3. A composition for light filtering, said composition comprising: a base material comprising a HEMA-based material; a plurality of plasmonic nanoparticles dispersed in the base material, the plurality of plasmonic nanoparticles exhibiting a peak optical absorption value in a range of about 500 nm to about 600 nm; an anchoring mechanism dispersed in the base material, the anchoring mechanism comprising a methacryloyl-derived monomer; and a nanoparticle coating material disposed on at least a portion of the plurality of plasmonic nanoparticles.

4. The base material is a) a biomaterial, or b) a biomaterial matrix, or c) a hydrogel, or d) a silicone-based hydrogel, or e) HEMA-based materials; The composition of claim 1 comprising:

5. The composition described in claim 1, wherein at least a portion of the plurality of gold nanoparticles include a spherical shape, a rod shape, a bipyramidal shape, or a star shape.

6. The composition described in claim 2, wherein at least a portion of the plurality of metal nanoparticles include a spherical shape, a rod shape, a bipyramidal shape, or a star shape.

7. 4. The composition of claim 3, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a spherical shape, a rod shape, a bipyramidal shape, a star shape, a decahedron shape, a cuboctahedron shape, or a cube shape.

8. The composition of claim 1, wherein at least a portion of the plurality of gold nanoparticles have a size ranging from about 1 nm to about 99 nm.

9. The composition of claim 2, wherein at least a portion of the plurality of metal nanoparticles have a size of about 1 nm to about 99 nm.

10. 4. The composition of claim 3, wherein at least a portion of the plurality of plasmonic nanoparticles comprises a size of from about 1 nm to about 99 nm.

11. The composition of claim 1 , wherein the fixation mechanism comprises glycidyl methacrylate.

12. The composition of claim 1 , wherein the nanoparticle coating material comprises poly(vinyl alcohol).

13. The composition of claim 2, wherein at least a portion of the plurality of metal nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm.

14. The composition of claim 3, wherein at least a portion of the plurality of plasmonic nanoparticles exhibit a full width at half maximum (FWHM) of about 30 nm to about 100 nm.

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