Expandable production of synthetic spicules and uses thereof

Abstract

A method of forming a synthetic brochosome is provided, the method comprising combining (i) a polymer solution comprising a solvent and an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, with (ii) an external fluid immiscible with the solvent, thereby forming droplets of the polymer solution in the external fluid; removing the external fluid and the solvent from the droplets, thereby providing a synthetic brochosome. Also provided is a synthetic brochosome and a composition comprising the synthetic brochosome.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 596,808, filed November 7, 2023, and U.S. Provisional Application No. 63 / 692,247, filed September 9, 2024, each of which is incorporated herein by reference in its entirety.

[0002] Government support terms This invention was carried out with government support under license number N00014-23-1-2173 granted by the United States Navy / ONR and license number IIP2111960 granted by the National Science Foundation. The government enjoys certain rights in this invention. Technical Field

[0003] The topics disclosed in this article relate to the high throughput, scalable preparation, and applications of monodisperse synthetic brochosomes. Background Technology

[0004] Brochosomes, considered one of the most complex natural structures, are three-dimensional, soccer ball-like microparticles produced by leafhoppers, with distributed nanoscale cavities (Day et al., "The Origin and Structure of Brochosomes,"). J Ultra Mol Struct R, 2:239-244, 1958; Rakitov et al., “Brochosomal coats turnleafhopper (Insecta, Hemiptera, Cicadellidae) integument to superhydrophobicstate,” Proc Roy Soc B-Biol Sci (280:20122391, 2013). In nature, leafhoppers use their stingers for a variety of purposes, including camouflage (Yang et al., “Ultra-antireflective synthetic brochosomes,”). Nat CommunThe properties of brochosomes (eLife 13: e103508, 2024) and their repellency (Rakitov et al., above) as well as some hypothetical functions (Rakitov et al., “What are brochosomes for? An enigma of leafhoppers (Hemiptera, Cicadellidae)”, Denisia 4:411-432, 2002) remain to be explored. A key fundamental step in integrating these attractive functions into artificial materials for real-world applications is the ability to mass-produce synthetic counterparts of natural brochosomes. Due to the highly complex geometry and micron and nanoscale dimensions of natural brochosomes, producing synthetic versions of brochosomes remains a significant technical challenge, even using state-of-the-art micron and nanon fabrication techniques.

[0005] In nature, leafhoppers use Malpighian tubules, highly coiled microscopic tubular structures responsible for producing spines. Specifically, Malpighian tubules can produce large populations of highly monodisperse natural spines with almost identical geometric characteristics within a leafhopper colony. However, existing micron and nanoscale manufacturing techniques cannot produce large quantities of monodisperse spine-like particles.

[0006] Therefore, there is a need for scalable methods for synthesizing spiky particles and preparing said particles. This disclosure at least partially satisfies these and other needs. Summary of the Invention

[0007] This disclosure relates to a scalable method for preparing synthetic spikes with customizable geometries using microfluidics and their applications. Inspired by the ability of martensitic tubes to generate large quantities of monodisperse spikes, this paper discloses a droplet-based microfluidic system that can be used to generate continuous monodisperse synthetic spikes in a highly scalable manner. The disclosed method comprises two parts: (1) the formation and emulsification of solvent droplets containing monodisperse polymers, and (2) the evaporation of polymer-containing solvent droplets through controlled interfacial instability and spontaneous emulsification processes to form synthetic spike particles.

[0008] The disclosed method is capable of producing large quantities (e.g., approximately >10) 5High-quality, monodisperse synthetic spikes (particles / second), having adjustable size and geometry very similar to that of natural spikes. These synthetic spikes can be used as 1) particles assembled on solid surfaces, 2) particles embedded in solid media, 3) particles assembled at fluid-fluid interfaces, or as 4) particles suspended in fluid media. These uses include, but are not limited to, (1) liquid-repellent coatings, (2) anti-reflective coatings, (3) white pigments, (4) ultraviolet (UV) filters or blocking agents, (5) particle scatterers and absorbers for light signal management, and (6) thermal characteristic management.

[0009] On one hand, a method for forming a synthetic spiky body is provided, the method comprising (i) combining a polymer solution comprising a solvent and an amphiphilic polymer with (ii) an external fluid immiscible with the solvent, thereby forming droplets of the polymer solution in the external fluid, the amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component; removing the external fluid and the solvent from the droplets, thereby providing a synthetic spiky body.

[0010] On the other hand, for oil-in-water emulsion systems, a synthetic needle is provided comprising an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, wherein the mass fraction of the hydrophilic polymer component is in the range of about 0.05 to about 0.45. On the other hand, a composition is provided comprising any of the disclosed synthetic needles and a carrier.

[0011] On the other hand, for water-in-oil emulsion systems, a synthetic needle is provided comprising an amphiphilic polymer having a hydrophilic polymer component and a hydrophobic polymer component, wherein the hydrophobic polymer component is in the range of about 0.05 to about 0.45 by mass fraction. On the other hand, a composition is provided comprising any of the disclosed synthetic needles and a carrier.

[0012] Other systems, methods, features, and / or advantages will or may become apparent to those skilled in the art upon examination of the following figures and detailed description. All such additional systems, methods, features, and / or advantages are intended to be included within this specification and protected by the appended claims. Attached Figure Description

[0013] Figure 1A-1FThe overall scalable fabrication process for monodisperse synthetic spikes using a droplet microfluidic system is illustrated. Figure 1A shows a schematic diagram of the microfluidic chip and droplet generation process in a flow-focused droplet generator. Figure 1B shows an optical microscope image of polymer-containing solvent droplets generated at the nozzle of the droplet generator. Figure 1C shows the evaporation process of the solvent droplets forming the spikes. Figure 1D shows the pores formed through an interfacial instability process. Figure 1E shows the structure of the amphiphilic polymer and typical operating ranges for forming synthetic spikes, such as hydrophilic and hydrophobic fractions, and molecular weight. Figure 1F shows the geometric parameters of the synthetic spikes.

[0014] Figure 2A-2C This illustrates highly monodisperse synthetic spikes prepared using a droplet microfluidic system, compared to other emulsification methods that form polydisperse spike-like particles. In Figure 2A, an electron micrograph shows a large number of monodisperse synthetic spikes prepared by a droplet microfluidic system that generates monodisperse solvent droplets. For other emulsification methods, solvent droplets are generated in water using a homogenizer. As shown in Figure 2B, polydisperse synthetic spikes are obtained due to the polydispersity of the solvent droplets generated by the homogenizer system. For the droplet microfluidic system, the synthetic spikes are made from PS dissolved in toluene at 0.2% (w / w). 109k -b-P4VP 27k The solvent droplets were prepared with a diameter of approximately 5 μm. For the homogenizer system, the same polymer at a concentration of 1% (w / w) was used in toluene and emulsified into surfactant-containing water at 14,000 rpm for 1 minute. Figure 2C shows a comparison of the particle size distribution of the synthetic spikes produced by the microfluidic system (solid line) and the homogenizer system (dotted line). In this specific example, the mean diameter and standard deviation of the synthetic spikes produced by the microfluidic system and the homogenizer system were 1177 nm ± 192 nm and 1519 ± 405 nm, respectively. Based on these measurements, the coefficients of variation of the synthetic spikes produced by the microfluidic system and the homogenizer system were 16.3% and 26.7%, respectively.

[0015] Figures 3A-3C The geometrically related preparation parameters and representative results obtained by changing these parameters are shown. Figure 3A shows the phase diagram of the morphology and pore size of the synthetic spikes, expressed as polymer molecular weight and hydrophilicity fraction. The pore size of the open-cell synthetic spikes is indicated in circles and in μm. Figures 3B-3C show electron micrographs illustrating different pore sizes of the synthetic spikes expressed as hydrophilicity fraction (Figure 3B) and polymer molecular weight (Figure 3C). In Figure 3B, the polymers have similar molecular weights (Figure 3B, Figure 3C, Figure ... n ), but using different hydrophilicity fractions ( HP Comparison: PS45k -b-P4VP 5.5k ( n = 50.5 kg / mol HP = 0.1) and PS 48k -b-P4VP 11k ( n = 59 kg / mol, HP = 0.19). The same concentration (1.28 mM) and solvent droplet size (approximately 4 μm) were used in the experiment. In Figure 3C, samples with similar values ​​were tested. HP but n Different polymers: PS from top to bottom in the image 190k -b-P4VP 45k PS 109k -b-P4VP 27k PS 48k -b-P4VP 11k PS 27k -b-P4VP 7k and PS 12k -b-P4VP 3.2k And their n The values ​​were 235 kg / mol, 136 kg / mol, 59 kg / mol, 34 kg / mol, and 15.2 kg / mol, respectively.

[0016] Figure 4A-4L Different morphologies obtained using the disclosed droplet microfluidic system are shown. Spike-like structures can be obtained by adjusting the preparation parameters within the system's operating range. In contrast, closed-pore, mixed-pore, micelle, or sac-like structures can be obtained outside the operating range. Electron micrographs in Figures 4A-4I show various geometries of spike-like structures with open pores, as well as other morphologies emerging from preparation parameters outside the operating range: closed pores (Figure 4J), mixed pores of open and closed pores (Figure 4K), and sac-like structures (Figure 4L). The polymers used in the experiments and their concentrations (% (w / w)) are in PS. 12k -b-P4VP 3.2k 0.02% (Figure 4A), PS 27k -b-P4VP 7k 0.04% (Figure 4B), PS 45k -b-P4VP 5.5k 0.075% (Figure 4C), PS 48k -b-P4VP 11k0.087% (Figure 4D), PS 89k -b-P4VP 26 k 0.17% (Figure 4E), PS 104k -b-P4VP 30k 0.2% (Figure 4F), PS 107k -b-P4VP 20k 0.19% (Figure 4G), PS 109k -b-P4VP 27k 0.2% (Figure 4H), PS 190k -b-P4VP 45k 0.1% (Figure 4I) and PS 40k -b-P4VP 5.6k 0.04% (Figure 4J), PS 447k -b-P4VP 110k 0.1% (Figure 4K), PS 47k -b-P4VP 25k 0.11% (Figure 4L), where the solvent droplet diameter is in the range of 5-10 μm.

[0017] Figures 5A-5B This shows the relationship with closed-pore spherical particles (PS) 40k -b-P4VP 5.6k (Figure 5B) Compared to highly porous synthetic needles (PS) 48k -b-P4VP 11k (Figure 5A) Electron micrograph of a cross section. The image was obtained using a combination of focused ion beam (FIB) and scanning electron microscopy.

[0018] Figures 6A-6B The effect of polymer concentration on the particle size of the resulting synthetic spikes is shown. As a representative case, different concentrations of PS were used within solvent droplets of the same size. 48k -b-P4VP 11k Synthetic spikes were prepared, and their particle size was measured based on electron micrographs (Figures 6A and 6B). The polymer concentrations tested in toluene were 0.04% (Figure 6A) and 0.174% (Figure 6B) (w / w), and the droplet size was approximately 5 μm in both cases. The resulting particle sizes were 499.53 ± 10.10 μm (Figure 6A) and 681.65 ± 24.99 μm (Figure 6B).

[0019] Figures 7A-7B The effect of solvent droplet size on the particle size of the resulting synthetic spikes is shown. The size of the solvent droplets was measured by imaging the nozzle region of the flow-focusing droplet generator using an optical microscope equipped with a high-speed camera. Figures 7A-7BOptical microscopic images (top row) of droplets generated from a 10 μm nozzle and electron micrographs (bottom row) of the resulting synthetic spike particles are shown. To compare particle size by varying droplet size, toluene solutions with the same polymer concentration were used: 0.04% (w / w) PS 27k -b-P4VP 3.2k (Figure 7A) and 0.04% (%w / w) PS 48k -b-P4VP 11k (Figure 7B). From left to right, the measured toluene droplet sizes were 4.3 μm and 6.74 μm (Figure 7A) and 5.32 μm and 9.97 μm (Figure 7B). The particle sizes obtained based on electron micrographs were 369.05 ± 13.94 μm and 469.48 ± 15.83 μm (Figure 7A), 524.02 ± 20.72 μm and 772.35 ± 24.43 μm (Figure 7B).

[0020] Figures 8A-8C The effect of molecular weight on the resulting particle size of the synthesized spikes is shown. To compare particle size by molecular weight, the same polymer concentration of 12.8 mM and a solvent droplet size of approximately 4 μm were used. Electron micrographs show the particle size obtained by PS... 27k -b-P4VP 3.2k (Figure 8A), PS 48k -b-P4VP 11k (Figure 8B) and PS 109k -b-P4VP 27k (Figure 8C) The synthetic spikes were prepared with molecular weights of 34 kg / mol, 59 kg / mol, and 136 kg / mol, respectively. The particle sizes, measured by electron microscopy, were 408.72 ± 21.74 μm (Figure 8A), 458.68 ± 28.10 μm (Figure 8B), and 881.34 ± 52.00 μm (Figure 8C).

[0021] Figures 9A-9C The effect of polymer concentration on the pore depth of the synthesized spikes is shown. Specifically, Figures 9A-9C It shows the PS 27k -b-P4VP 3.2kElectron micrographs of synthetic spikes prepared in toluene at different concentrations. To compare the effect of polymer concentration on the pore depth of the synthetic spikes, bidisperse toluene droplets with diameters of approximately 3.50 μm and approximately 6.60 μm were generated using different polymer concentrations of 0.01% (Fig. 9A), 0.04% (Fig. 9B), and 0.2% (Fig. 9C) (w / w), and evaporated under the same conditions (rapid evaporation was prevented by mixing with a toluene-water emulsion). The bidisperse toluene droplets were used to demonstrate that the effect of polymer concentration is independent of the size of the solvent droplets. Below a certain polymer concentration (approximately 0.04% (w / w)), a decrease in pore depth was observed.

[0022] Figures 10A-10B The effect of evaporation rate on pore formation of the synthetic spikes is shown. To adjust the evaporation rate, polymer-containing toluene droplets were mixed with surfactant-containing DI water (Fig. 10A) and water-in-toluene emulsions (Fig. 10B) and evaporated under the same humidity and temperature. To compare the evaporation effects, the same manufacturing parameters, such as polymer type (PS), were used. 48k -b-P4VP 11k The concentration (0.04% (w / w)) and droplet size (approximately 4.94 μm) were measured. Complete evaporation was observed to take approximately 1 minute for the DI aqueous solution and approximately 5 hours for the emulsion mixture. Due to rapid evaporation, the pore depth of particles formed in the DI aqueous solution was negligible (Fig. 10A), while the synthetic spikes formed in the emulsion mixture showed significant pore formation (Fig. 10B).

[0023] Figure 11A-11C The morphological transformation of the surface pores is shown. Scanning electron micrographs reveal various pore morphologies of the synthetic spikes: circular (Fig. 11A), polygonal (Fig. 11B), and amorphous (Fig. 11C) pores. The synthetic spikes were fabricated using three different amphiphilic polymers that produce different solvent-water interfacial tensions: PS 190k -b-P4VP 45k The value is 4.10 ± 0.06 mN / m (FIG. 11A), PS 48k -b-P4VP 11k The value is 3.45 ± 0.12 mN / m (Figure 11B), and PS 37k -b-P4VP 10.5k The value is 2.27 ± 0.56 mN / m (Figure 11C). The scale bar is 500 nm.

[0024] Figure 12 The diagram illustrates the morphological transformation of holes from circular to polygonal and from circular to amorphous. A schematic diagram shows the geometry of a water droplet forming a surface hole, which is used as a model system to calculate the critical interfacial tension for hole morphological transformation.

[0025] Figures 13A-13B The morphological transformation of surface pores is shown. Scanning electron microscopy of cross-sections of particles produced using two different amphiphilic polymers is presented. The inset shows the surface morphology of the particles. The particles were cross-sectioned using a focused ion beam (FIB). Note the deformation of the particle cross-section due to ion beam exposure. Particles with circular surface pores also show spherical internal pores (Fig. 13A), and particles with a honeycomb-like surface morphology show faceted internal pores (Fig. 13B). The polymers constituting the particles and the measured interfacial tensions are PS. 45k -b-P4VP 5.5k The value was 3.89 ± 0.03 mN / m (Figure 13A), and PS 48k -b-P4VP 11k The value is 3.45 ± 0.12 mN / m (Figure 13B). Scale bar: 500 nm.

[0026] Figures 14A-14B The degree of amorphism of the pores is shown. Scanning electron microscopy of particles produced using synthetic leafhopper systems with two different amphiphilic polymers shows that their pore morphologies exhibit lower (Fig. 14A) and higher (Fig. 14B) amorphous characteristics. The polymers constituting the particles and the measured interfacial tensions are PS. 12k -b-P4VP 3.2k It is 2.74 ± 0.75 mN / m (Figure 14A), and PS 37k -b-P4VP 10.5k The value is 2.27 ± 0.56 mN / m (Figure 14B). Scale bar: 500 nm.

[0027] Figure 15 Interfacial tension and pore morphology are shown. The phase diagram illustrates the relationship between the formation of various pore morphologies of the synthesized thorns and the molecular weight and hydrophilicity fraction of PS-b-P4VP in the presence of a 0.4 wt% SDS aqueous solution. The interfacial tension at the water-solvent interface varies with the molecular weight of PS-b-P4VP and its hydrophilicity fraction. Dark gray and light gray shaded areas indicate the formation of ribbed straight thorns (…). P. striatus ) and cuckoo leafhopper ( G. fennahi The molecular weight range of proteins in the natural stinger.

[0028] Figures 16A-16DThe antireflective properties of the synthetic spikes are shown. Figure 16A shows the reflectance spectrum, and Figure 16B shows the reduced reflectance of the coated (dashed line) and uncoated (dotted line) synthetic spikes compared to an Au reflector (solid line) used as a control. The coated spikes were coated with a 30 nm thick Au sputtering layer. The incident angle was 6°. The reduced reflectance spectrum was normalized using the spectrum from the gold reflector. The morphology of the synthetic spikes is shown in electron micrographs in Figure 16C (coated synthetic spikes) and Figure 16D (uncoated synthetic spikes).

[0029] Figures 17A-17B The use of synthetic spikes as a white pigment is illustrated. Figure 17A shows the diffuse reflectance spectra of the synthetic spikes (solid lines) and titanium dioxide (dashed lines) in the visible wavelength range. It should be noted that titanium dioxide is used as a commercial white pigment. Figure 17B shows electron micrographs of TiO2 (dashed lines) and the synthetic spikes (solid lines). The inset shows an optical image of the deposit on a silicon wafer, demonstrating its bright whiteness. Scale bar: 5 mm.

[0030] Figure 18 The application of the synthetic spike as a UV filter is shown. The transmission spectrum of the synthetic spike (dashed line) is compared with that of a quartz microscope slide (solid line). The inset shows an electron micrograph illustrating the structure of the synthetic spike used in the experiment.

[0031] Figures 19A-19D The use of synthetic spikes in optical feature management applications is illustrated, particularly in terms of directional visibility. Figures 19A-19B show schematic images of the experimental setup illustrating directional vision when viewed from the absorbing plume side (Figure 19A) and the scattering plume side (Figure 19B). A masking agent is dispersed in a fluid medium contained in a cuvette to simulate an atmospheric plume. Figures 19C-19D are electron micrographs showing two different types of scatterers compared in the experiment: a synthetic spike (Figure 19C) and a non-porous sphere (Figure 19C). Scale bar is 1 μm.

[0032] Figures 20A-20E The efficiency of two different light-scattering masking agents is compared: synthetic spikes and non-porous spheres. Figures 20A-20B are optical images showing the following two different scatterers at different concentrations (from 2 × 10⁻⁶). 9Views of the absorber and scattering sides at initial concentration dilutions (particles / mL (100%)): synthetic spikes (Fig. 20A) and non-porous spheres (Fig. 20B). Fig. 20C is a graph showing the concentration ranges achieving directional vision for each type of scatterer. The synthetic spike masking agent exhibited directional vision in the dilution range of 89% to 14%, while the non-porous spheres achieved directional vision between 14% and 3%. Fig. 20D is a graph showing the contrast (Cab / Csc) between the absorber and scatterer sides, comparing the synthetic spikes (blue line) and non-porous spheres (green line) as scatterers. Fig. 20E is a graph showing the settling time of synthetic spikes and non-porous spheres with different particle sizes over a distance of 1 meter.

[0033] Figures 21A-21B The application of synthetic spiky particles as fluorescent particle tracers is illustrated. Figure 21A shows an optical fluorescence image of synthetic spiky particles loaded with pyrene, and Figure 21B shows an electron micrograph of them. To incorporate the fluorescent dye, PS... 109k -b-P4VP 27k Water-insoluble pyrene was dissolved in toluene and flowed into a microfluidic system to generate droplets that form spikes. Evaporation of the polymer and the pyrene-containing droplets yielded blue fluorescent synthetic spikes.

[0034] Figure 22 A graph depicts the flow rates of solvent (e.g., toluene) and water in a 10 μm nozzle droplet generator, along with the corresponding droplet generation modes: monodisperse (colored filled cells), bisperse (undecorated cells), and polydisperse (patterned cells). The graph indicates some measured values ​​for droplet size and throughput. Flow rates were measured by thermal flow sensors (Elveflow, MFS 1, 2, 3), and the graph is based on the water flow rate measured by MFS3 and the toluene flow rate measured by MFS1. The slanted letters indicate the flow rate measured by MFS 2. Detailed Implementation

[0035] The invention can be more readily understood by referring to the following specific embodiments and the examples and drawings included therein.

[0036] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it should be understood that, unless otherwise specified, this disclosure is not limited to specific synthetic methods, or, unless otherwise specified, is not limited to specific reagents, as these can certainly vary. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the invention, exemplary methods and materials are described hereafter.

[0037] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with the cited publications. The publications discussed herein are provided only for informational purposes prior to the filing date of this application. Nothing herein should be construed as an admission that the invention is not entitled to precedence over such publications by virtue of prior art. Furthermore, the publication dates provided herein may differ from the actual publication dates, which may require independent verification.

[0038] It should be understood that, for clarity, certain features of this disclosure described in the context of a single aspect may also be provided in combination within that single aspect. Conversely, for brevity, various features of this disclosure described in the context of a single aspect may also be provided individually or in any suitable sub-combination. 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. Methods and materials similar to or equivalent to those described herein may be used to practice or test the contents of this disclosure.

[0039] definition Throughout this specification and the following claims, numerous terms will be referenced, and these terms should be defined to have the following meanings: Throughout the description and claims of this specification, the word “comprise” and other forms of the word, such as “comprising” and “comprises”, mean “including but not limited to” and are not intended to exclude, for example, other additives, segments, wholes, or steps. Furthermore, it should be understood that the terms “comprise,” “comprising,” and “comprises”, because they relate to various aspects, elements, and features of the disclosed invention, also include the more limited aspects of “consisting substantially of” and “comprises of”.

[0040] As used herein, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural indicators. Thus, for example, unless the context clearly indicates otherwise, references to “polymer” include aspects having two or more such polymers.

[0041] In this document, a range may be expressed as from “about” a specific value and / or to “about” another specific value. When expressing such a range, the other side includes from said one specific value and / or to said other specific value. Similarly, when a value is expressed as an approximation using the antecedent “about”, it should be understood that said specific value forms the other side. It should be further understood that each endpoint of the range is significant relative to and independent of the other endpoint. The term “about” may also mean within 5% of the value, for example, within 4%, 3%, 2%, 1%, or 0.5%.

[0042] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes examples of the event or situation occurring as well as examples of the event or situation not occurring.

[0043] References to the weight parts of a specific element or component in the composition in the specification and the final claims indicate the weight relationship between the element or component in the composition or article and any other element or component, expressed as parts by weight. Therefore, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a 2:5 weight ratio (% w / w), and are present in such a ratio regardless of whether the compound contains other components.

[0044] In the specification and concluding claims, references to the volume parts of a specific element or component in a composition indicate the volume relationship between that element or component and any other element or component, expressed as volume parts. Therefore, in a compound containing 2 volume parts of component X and 5 volume parts of component Y, X and Y are present in a 2:5 volume ratio (% v / v), and are present in such a ratio regardless of whether the compound contains other components.

[0045] The terms “for example” and “as” and their grammatical equivalents, unless otherwise explicitly stated, should be understood to be followed by the phrase “and not limited to”.

[0046] method On one hand, a method for forming a synthetic spiky body is provided, the method comprising (i) combining a polymer solution comprising a solvent and an amphiphilic polymer with (ii) an external fluid immiscible with the solvent, thereby forming droplets of the polymer solution in the external fluid, the amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component; removing the external fluid and the solvent from the droplets, thereby providing a synthetic spiky body.

[0047] In some specific examples, the droplets have diameters ranging from approximately 100 nm to approximately 1000 µm, including approximately 200 nm, approximately 300 nm, approximately 400 nm, 500 nm, approximately 600 nm, approximately 700 nm, approximately 800 nm, approximately 900 nm, approximately 1 µm, approximately 2 µm, approximately 3 µm, approximately 4 µm, approximately 5 µm, approximately 6 µm, approximately 7 µm, approximately 8 µm, approximately 9 µm, approximately 10 µm, approximately 11 µm, approximately 12 µm, approximately 13 µm, approximately 14 µm, and approximately 15 µm. Exemplary values ​​for m, approximately 16µm, approximately 17µm, approximately 18µm, approximately 19µm, approximately 20µm, approximately 25µm, approximately 30µm, approximately 35µm, approximately 40µm, approximately 45µm, approximately 50µm, approximately 60µm, approximately 70µm, approximately 80µm, approximately 90µm, approximately 100µm, approximately 200µm, approximately 300µm, approximately 400µm, approximately 500µm, approximately 600µm, approximately 700µm, approximately 800µm, approximately 900µm, and approximately 1000µm.

[0048] In some specific examples, the polymer solution and an external fluid are combined within the microfluidic device. In some specific examples, the microfluidic device geometry can encompass crossflow, co-flow, and flow-focusing configurations. For flow-focusing devices, the nozzle has a diameter from about 1 µm to about 1000 µm, including about 2 µm, about 3 µm, about 4 µm, about 5 µm, about 6 µm, about 7 µm, about 8 µm, about 9 µm, about 10 µm, about 11 µm, about 12 µm, about 13 µm, about 14 µm, about 15 µm, about 16 µm, about 17 µm, about 18 µm, about 19 µm, about 20 µm, about 25 µm, about 30 µm, about 35 µm, about 40 µm, about 45 µm, and so on. Exemplary values ​​of 50µm, about 60µm, about 70µm, about 80µm, about 90µm, about 100µm, about 110µm, about 120µm, about 130µm, about 140µm, about 150µm, about 160µm, about 170µm, about 180µm, about 190µm, about 200µm, about 300µm, about 400µm, about 500µm, about 600µm, about 700µm, about 800µm, about 900µm, and about 1000µm.

[0049] In some specific examples, the solvent and external fluid are removed from the droplets by evaporation, lyophilization, centrifugation, or any combination thereof. In some specific examples, the synthetic spikes are rinsed, dried, suspended in a liquid medium, or any combination thereof.

[0050] In some specific examples, the method includes forming an oil-in-water emulsion with a solvent and an external fluid; wherein the solvent is at a concentration of about 0% v / v to about 99% v / v; and wherein a polymer solution is added to the emulsion. Here, the solvent forms oil droplets (dispersed phase) in the aqueous external fluid (continuous phase). In some specific examples, the solvent is at a concentration of about 1% to about 95% v / v, or about 5% to about 85% v / v, or about 10% to about 70% v / v, or about 15% to about 75% v / v, or about 25% to about 65% v / v, or about 35% to about 55% v / v, or about 30% to about 40% v / v, or about 1% to about 40% v / v, or about 5% to about 30% v / v, or about 10% to about 25% v / v, or about 55% to about 95% v / v, or about 65% to about 85% v / v. In some specific examples, the solvent is nonpolar and the external fluid is polar, and the solvent is emulsified in the external fluid to form an oil-in-water emulsion.

[0051] In some specific examples, the hydrophilic polymer component is present in a mass fraction of about 0.05 to about 0.45, including exemplary values ​​of about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35 and about 0.4.

[0052] In other specific examples, the method comprises forming a water-in-oil emulsion with a solvent and an external fluid; wherein the solvent is at a concentration of about 0% v / v to about 99% v / v; and wherein a polymer solution is added to the emulsion. Here, the solvent forms water droplets (dispersed phase) in an oily external fluid (continuous phase). In some specific examples, the solvent is at a concentration of about 1% to about 95% v / v, or about 5% to about 85% v / v, or about 10% to about 70% v / v, or about 15% to about 75% v / v, or about 25% to about 65% v / v, or about 35% to about 55% v / v, or about 30% to about 40% v / v, or about 1% to about 40% v / v, or about 5% to about 30% v / v, or about 10% to about 25% v / v, or about 55% to about 95% v / v, or about 65% to about 85% v / v. In some specific examples, the solvent is polar and the external fluid is nonpolar, and the solvent is emulsified in the external fluid to form a water-in-oil emulsion.

[0053] In some specific examples, the hydrophobic polymer component is present in a mass fraction of about 0.05 to about 0.45, including exemplary values ​​of about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35 and about 0.4.

[0054] In some specific examples, the solvent is toluene, acetone, pentane, hexane, cyclohexane, heptane, octane, isooctane, nonane, decane, undecane, dodecane, hexadecane, dimethyl carbonate, chloroform, dichloromethane, benzene, silicone oil, tetrahydrofuran, xylene, trichloroethylene, methyl tert-butyl ether (MTBE), methyl ethyl ketone (MEK), methanol, ethanol, isopropanol, butanol, hexanol, octanol dimethylformamide, dichloroethane, carbon tetrachloride, water, or any combination thereof.

[0055] In some specific examples, the external fluid is water. In some specific examples, the external fluid further comprises a surfactant. In some specific examples, the surfactant is sodium dodecyl sulfate (SDS), poly(vinyl alcohol) (PVA), hexadecyltrimethylammonium bromide (CTAB), sorbitan monooleate (Span 80), sorbitan monostearate (Span 60), polyethylene glycol sorbitan monolaurate (Tween 20), 1H,1H,2H,2H-perfluoro-1-octanol (PFO), or any combination thereof. In some specific examples, the surfactant in the external phase ranges from about 0.05% w / w to about 0.8% w / w, including exemplary values ​​of about 0.1% w / w, about 0.15% w / w, about 0.2% w / w, about 0.25% w / w, about 0.3% w / w, about 0.35% w / w, about 0.4% w / w, about 0.45% w / w, about 0.5% w / w, about 0.55% w / w, about 0.6% w / w, about 0.65% w / w, about 0.7% w / w, and about 0.75% w / w.

[0056] In some specific examples, the amphiphilic polymers are poly(styrene)-b-poly(4-vinylpyridine), poly(styrene)-b-poly(acrylic acid), poly(styrene)-b-poly(vinyl alcohol), poly(D-lactide)-polyethylene glycol methyl ether, polyethylene glycol-poly(lactide-co-lactide), poly(D,L-lactide), polylactide-polyethylene glycol-COOH, poly(ethylene glycol) methyl ether-block-poly(D,L-lactide), methoxy poly(ethylene glycol)-b-poly( Caprolactone), carboxylic acid poly(ethylene glycol)-block-poly(lactide-co-lactide), methoxy poly(ethylene glycol)-b-poly(lactide-co-lactide), methoxy (polyethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(D,L-lactide), amphiphilic bottle brush block copolymers, amphiphilic copolymers based on PolyPEG-stearic acid, amphiphilic proteins, or any combination thereof.

[0057] In some specific examples, the amphiphilic polymers have a number-average molecular weight of about 1 kg / mol to about 1000 kg / mol, including about 2 kg / mol, about 3 kg / mol, about 4 kg / mol, about 5 kg / mol, about 6 kg / mol, about 7 kg / mol, about 8 kg / mol, about 9 kg / mol, about 10 kg / mol, about 20 kg / mol, about 30 kg / mol, about 40 kg / mol, about 50 kg / mol, about 60 kg / mol, about 70 kg / mol, about 80 kg / mol, about 90 kg / mol, about 100 kg / mol, about 125 kg / mol, about 150 kg / mol, and about 175 kg / mol. Exemplary values ​​for ol, about 200 kg / mol, about 225 kg / mol, about 250 kg / mol, about 275 kg / mol, about 300 kg / mol, about 325 kg / mol, about 350 kg / mol, about 375 kg / mol, about 400 kg / mol, about 425 kg / mol, about 450 kg / mol, about 475 kg / mol, about 500 kg / mol, about 550 kg / mol, about 600 kg / mol, about 650 kg / mol, about 700 kg / mol, about 750 kg / mol, about 800 kg / mol, about 850 kg / mol, about 900 kg / mol, and about 950 kg / mol.

[0058] In some specific examples, the synthetic spikes have particle sizes from about 100 nm to about 20 µm, including about 125 nm, about 150 nm, about 175 nm, about 200 nm, about 225 nm, about 250 nm, about 275 nm, about 300 nm, about 325 nm, about 350 nm, about 375 nm, about 400 nm, about 425 nm, about 450 nm, about 475 nm, and about 500 nm. Exemplary values ​​of approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 850nm, approximately 900nm, approximately 950nm, approximately 1µm, approximately 2µm, approximately 3µm, approximately 4µm, approximately 5µm, approximately 6µm, approximately 7µm, approximately 8µm, approximately 9µm, approximately 10µm, approximately 12µm, approximately 14µm, approximately 16µm, or approximately 18µm.

[0059] In some specific examples, the synthetic spiky has a pore size of about 20 nm to about 5 µm, including exemplary values ​​of about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 125 nm, about 150 nm, about 175 nm, about 200 nm, about 225 nm, about 250 nm, about 275 nm, about 300 nm, about 325 nm, about 350 nm, about 375 nm, about 400 nm, about 425 nm, about 450 nm, about 475 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 µm, about 1.5 µm, about 2 µm, about 2.5 µm, about 3 µm, about 3.5 µm, about 4.0 µm, and about 4.5 µm.

[0060] In some specific examples, the synthetic spikes have pore depths of approximately 10 nm to approximately 5 µm, including approximately 20 nm, approximately 30 nm, approximately 40 nm, approximately 50 nm, approximately 60 nm, approximately 70 nm, approximately 80 nm, approximately 90 nm, approximately 100 nm, approximately 125 nm, approximately 150 nm, approximately 175 nm, approximately 200 nm, approximately 225 nm, approximately 250 nm, approximately 275 nm, approximately 300 nm, approximately 325 nm, approximately 350 nm, and approximately... Exemplary values ​​for 375nm, approximately 400nm, approximately 425nm, approximately 450nm, approximately 475nm, approximately 500nm, approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 850nm, approximately 900nm, approximately 950nm, approximately 1µm, approximately 1.5µm, approximately 2µm, approximately 2.5µm, approximately 3µm, approximately 3.5µm, approximately 4.0µm, and approximately 4.5µm.

[0061] In some specific examples, the synthetic needles have a porosity of about 0.1 to 0.9, including about 0.12, about 0.14, about 0.16, about 0.18, about 0.2, about 0.22, about 0.24, about 0.26, about 0.28, about 0.3, about 0.31, about 0.34, about 0.36, about 0.38, about 0.4, about 0.42, about 0.44, and about 0. Exemplary values ​​are 0.46, approximately 0.48, approximately 0.5, approximately 0.52, approximately 0.54, approximately 0.56, approximately 0.58, approximately 0.6, approximately 0.62, approximately 0.64, approximately 0.66, approximately 0.68, approximately 0.70, approximately 0.72, approximately 0.74, approximately 0.76, approximately 0.78, approximately 0.8, approximately 0.82, approximately 0.84, approximately 0.86, and approximately 0.88. Here, porosity is defined as the volume percentage of voids within the synthetic thorn and expressed as a fraction between 0 and 1.

[0062] In some specific examples, the synthetic spikes have wall thicknesses from about 10 nm to about 2 µm, including about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 110 nm, about 120 nm, about 130 nm, about 140 nm, about 150 nm, about 160 nm, about 170 nm, about 180 nm, about 190 nm, about 200 nm, about 250 nm, and about 3 µm. Exemplary values ​​for 00nm, approximately 350nm, approximately 400nm, approximately 450nm, approximately 500nm, approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 900nm, approximately 1000nm, approximately 1100nm, approximately 1200nm, approximately 1300nm, approximately 1400nm, approximately 1500nm, approximately 1600nm, approximately 1700nm, approximately 1800nm, and approximately 1900nm.

[0063] An exemplary method is as follows. First, the polymer forming the spike is dissolved in a solvent medium (e.g., toluene) and flowed through a microfluidic system containing a flow-focusing droplet generator. The polymer-containing solvent forms droplets at cross-junctions that are compressed by an external flow of an immiscible fluid (e.g., water) containing a surfactant. The surfactant stabilizes the interface between the solvent and the external fluid and facilitates pore formation during solvent evaporation in the following process. The droplet size can be controlled by the nozzle size and the flow rates of the polymer-containing solvent and the external immiscible fluid; while the morphology of the synthesized spike can be controlled by the percentage of the hydrophilic portion of the amphiphilic polymer, its molecular weight, and the evaporation rate of the solvent droplets. Monodisperse polymer droplets are then collected at the outlet of the microfluidic system, and the solvent is subsequently dried, resulting in the formation of the spike structure through an interfacial instability process. During evaporation, both the amphiphilic polymer molecules and the surfactant are simultaneously adsorbed on the droplet surface, which reduces the interfacial tension at the solvent-immiscible interface. As the interfacial tension decreases, the droplet surface deforms to form a secondary submicron curvature, which allows external fluids to penetrate into the solvent droplet forming pores after the solvent droplet has completely evaporated.

[0064] Composition On one hand, a synthetic spiky body is provided, comprising an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, wherein the hydrophilic polymer component is present in a mass fraction of about 0.05 to about 0.45, including exemplary values ​​of about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35, and about 0.4. Hydrophobicity is defined as an equilibrium water contact angle greater than or equal to 90 degrees; while hydrophilicity is defined as an equilibrium water contact angle less than 90 degrees. In some specific examples, the hydrophobic polymer component is present in a mass fraction of about 0.95 to about 0.55, including exemplary values ​​of about 0.9, about 0.85, about 0.8, about 0.75, about 0.7, about 0.65, and about 0.6.

[0065] On the other hand, a synthetic spiky body is provided comprising an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, wherein the hydrophobic polymer component is present in a mass fraction of about 0.05 to about 0.45, including exemplary values ​​of about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35, and about 0.4. In some specific examples, the hydrophilic polymer component is present in a mass fraction of about 0.95 to about 0.55, including exemplary values ​​of about 0.9, about 0.85, about 0.8, about 0.75, about 0.7, about 0.65, and about 0.6.

[0066] In some specific examples, the amphiphilic polymers are poly(styrene)-b-poly(4-vinylpyridine), poly(styrene)-b-poly(acrylic acid), poly(styrene)-b-poly(vinyl alcohol), poly(D-lactide)-polyethylene glycol methyl ether, polyethylene glycol-poly(lactide-co-lactide), poly(D,L-lactide), polylactide-polyethylene glycol-COOH, poly(ethylene glycol) methyl ether-block-poly(D,L-lactide), methoxy poly(ethylene glycol)-b-poly( Caprolactone), carboxylic acid poly(ethylene glycol)-block-poly(lactide-co-lactide), methoxy poly(ethylene glycol)-b-poly(lactide-co-lactide), methoxy (polyethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(D,L-lactide), amphiphilic bottle brush block copolymers, amphiphilic copolymers based on PolyPEG-stearic acid, amphiphilic proteins, or any combination thereof.

[0067] In some specific examples, the amphiphilic polymers have a number-average molecular weight of about 1 kg / mol to about 1000 kg / mol, including about 2 kg / mol, about 3 kg / mol, about 4 kg / mol, about 5 kg / mol, about 6 kg / mol, about 7 kg / mol, about 8 kg / mol, about 9 kg / mol, about 10 kg / mol, about 20 kg / mol, about 30 kg / mol, about 40 kg / mol, about 50 kg / mol, about 60 kg / mol, about 70 kg / mol, about 80 kg / mol, about 90 kg / mol, about 100 kg / mol, about 125 kg / mol, about 150 kg / mol, and about 175 kg / mol. Exemplary values ​​for ol, about 200 kg / mol, about 225 kg / mol, about 250 kg / mol, about 275 kg / mol, about 300 kg / mol, about 325 kg / mol, about 350 kg / mol, about 375 kg / mol, about 400 kg / mol, about 425 kg / mol, about 450 kg / mol, about 475 kg / mol, about 500 kg / mol, about 550 kg / mol, about 600 kg / mol, about 650 kg / mol, about 700 kg / mol, about 750 kg / mol, about 800 kg / mol, about 850 kg / mol, about 900 kg / mol, and about 950 kg / mol.

[0068] In some specific examples, the synthetic spikes have particle sizes from about 100 nm to about 20 µm, including about 125 nm, about 150 nm, about 175 nm, about 200 nm, about 225 nm, about 250 nm, about 275 nm, about 300 nm, about 325 nm, about 350 nm, about 375 nm, about 400 nm, about 425 nm, about 450 nm, about 475 nm, and about 500 nm. Exemplary values ​​of approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 850nm, approximately 900nm, approximately 950nm, approximately 1µm, approximately 2µm, approximately 3µm, approximately 4µm, approximately 5µm, approximately 6µm, approximately 7µm, approximately 8µm, approximately 9µm, approximately 10µm, approximately 12µm, approximately 14µm, approximately 16µm, or approximately 18µm.

[0069] In some specific examples, the synthetic spiky has a pore size of about 20 nm to about 5 µm, including exemplary values ​​of about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 125 nm, about 150 nm, about 175 nm, about 200 nm, about 225 nm, about 250 nm, about 275 nm, about 300 nm, about 325 nm, about 350 nm, about 375 nm, about 400 nm, about 425 nm, about 450 nm and about 475 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 µm, about 1.5 µm, about 2 µm, about 2.5 µm, about 3 µm, about 3.5 µm, about 4.0 µm and about 4.5 µm.

[0070] In some specific examples, the synthetic spikes have pore depths of approximately 10 nm to approximately 5 µm, including approximately 20 nm, approximately 30 nm, approximately 40 nm, approximately 50 nm, approximately 60 nm, approximately 70 nm, approximately 80 nm, approximately 90 nm, approximately 100 nm, approximately 125 nm, approximately 150 nm, approximately 175 nm, approximately 200 nm, approximately 225 nm, approximately 250 nm, approximately 275 nm, approximately 300 nm, approximately 325 nm, approximately 350 nm, and approximately... Exemplary values ​​for 375nm, approximately 400nm, approximately 425nm, approximately 450nm, approximately 475nm, approximately 500nm, approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 850nm, approximately 900nm, approximately 950nm, approximately 1µm, approximately 1.5µm, approximately 2µm, approximately 2.5µm, approximately 3µm, approximately 3.5µm, approximately 4.0µm, and approximately 4.5µm.

[0071] In some specific examples, the synthetic needles have a porosity of about 0.1 to 0.9, including about 0.12, about 0.14, about 0.16, about 0.18, about 0.2, about 0.22, about 0.24, about 0.26, about 0.28, about 0.3, about 0.31, about 0.34, about 0.36, about 0.38, about 0.4, about 0.42, about 0.44, and about 0. Exemplary values ​​are 0.46, approximately 0.48, approximately 0.5, approximately 0.52, approximately 0.54, approximately 0.56, approximately 0.58, approximately 0.6, approximately 0.62, approximately 0.64, approximately 0.66, approximately 0.68, approximately 0.70, approximately 0.72, approximately 0.74, approximately 0.76, approximately 0.78, approximately 0.8, approximately 0.82, approximately 0.84, approximately 0.86, and approximately 0.88. Here, porosity is defined as the volume percentage of voids within the synthetic thorn and expressed as a fraction between 0 and 1.

[0072] In some specific examples, the synthetic needle has a circular hole. In other specific examples, the synthetic needle has a polygonal hole (e.g., a triangular hole, a square hole, a pentagonal hole, a hexagonal hole, a heptagonal hole, and an octagonal hole). In yet another specific example, the synthetic needle has an amorphous hole.

[0073] In some specific examples, the synthetic spikes have wall thicknesses from about 10 nm to about 2 µm, including about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 110 nm, about 120 nm, about 130 nm, about 140 nm, about 150 nm, about 160 nm, about 170 nm, about 180 nm, about 190 nm, about 200 nm, about 250 nm, and about 3 µm. Exemplary values ​​for 00nm, approximately 350nm, approximately 400nm, approximately 450nm, approximately 500nm, approximately 550nm, approximately 600nm, approximately 650nm, approximately 700nm, approximately 750nm, approximately 800nm, approximately 900nm, approximately 1000nm, approximately 1100nm, approximately 1200nm, approximately 1300nm, approximately 1400nm, approximately 1500nm, approximately 1600nm, approximately 1700nm, approximately 1800nm, and approximately 1900nm.

[0074] On the other hand, a composition is provided comprising any of the disclosed synthetic needles and a carrier. In some aspects, the composition is a coating, pigment, detergent, powder, or granules.

[0075] Example The following embodiments are provided to provide those skilled in the art with a complete disclosure and description of how to manufacture and evaluate the compounds, compositions, articles, apparatus, and / or methods claimed herein, and are intended merely as illustrative of the invention and not to limit the scope to which the inventors believe their invention belongs. However, based on this disclosure, those skilled in the art will understand that many changes can be made to the specific embodiments disclosed without departing from the spirit and scope of the invention and still obtaining the same or similar results.

[0076] Efforts have been made to ensure the accuracy of figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be taken into account. Unless otherwise specified, parts are by weight, temperatures are in °C or at ambient temperature, and pressures are at or near atmospheric pressure.

[0077] Example 1 - Synthesis of Spikes polymer:Amphiphilic polymers were used as raw materials for the synthesis of spurs. The amphiphilic polymers contain both hydrophobic and hydrophilic polymeric portions or domains, referred to herein as components, wherein for oil-in-water emulsion systems, the hydrophilic polymeric component ranges from 0.05 to 0.45. Hydrophobicity is defined as an equilibrium water contact angle greater than or equal to 90 degrees; while hydrophilicity is defined as an equilibrium water contact angle less than 90 degrees. Table 1 lists the polymers tested. Mass fraction of hydrophilic polymer ( HP It can be estimated by the following formula: in M n and M HP These are the number-average molecular weight of the polymer and the molecular weight of the hydrophilic portion of the amphiphilic polymer, respectively.

[0078] The polydispersity index (PDI) measures the molecular weight distribution within a polymer sample and is defined as the weight-average molecular weight (M). w ) and number-average molecular weight (M n The ratio of ).

[0079] In some specific examples, the PDI of the amphiphilic polymer forming the synthetic thorn with uniform pores ranges from about 1 to 1.5, including exemplary values ​​of about 1.05, about 1.1, about 1.15, about 1.2, about 1.25, about 1.3, about 1.35, about 1.4 and about 1.45.

[0080] Table 1. List of polymers and their properties, including pore size and wall thickness obtained when forming synthetic spikes.

[0081] Solvent: The dispersed liquid can be a nonpolar solvent for dissolving the polymer (oil-in-water system) or a polar solvent for dissolving water-soluble polymers (water-in-oil system). The solvent should be immiscible with the external fluid and have a vapor pressure higher than that of the external fluid. A vapor pressure difference of more than 1 mmHg between the two fluids is recommended. Toluene is used in all the following experiments unless otherwise specified.

[0082] Surfactants: Surfactants are used to stabilize emulsified liquids and induce interfacial instabilities. Typically, ionic surfactants are used in oil-in-water systems, and nonionic surfactants are used in water-in-oil systems. Sodium dodecyl sulfate (SDS) is used in all the following experiments unless otherwise specified.

[0083] As an illustrative example, to prepare the polymer solution that forms the spikes, 0.01-1% (w / w) of the polymer (PS-b-P4VP) was dissolved in a solvent (e.g., toluene) using a magnetic stirrer. After the polymer was completely dissolved in the solvent, the polymer-containing solvent was delivered to a tank connected to a microfluidic system. Then, a microfluidic droplet generator (Elveflow, microfluidic droplet pack) with a flow-focusing glass microfluidic chip (Micronit) was used to generate oil-in-water droplets of various nozzle diameters (e.g., a 10 μm nozzle for generating droplets with a diameter of 4-15 μm). The inlet of the droplet generator was connected to two different tanks: one for the droplet phase (polymer-containing toluene) and the other for the continuous phase (DI water containing surfactant), wherein the surfactant concentration was in the range of 0.2-0.8% (w / w). The outlet was connected to a glass tank for droplet collection. Before droplet formation, the glass reservoir at the outlet is filled with a water-in-solvent emulsion to maintain the stability of the microfluidic system and allow the polymer-containing solvent droplets to evaporate slowly. The solvent concentration of the emulsion can vary from 0-40% v / v, depending on the polymer concentration in the solvent droplets. The flow rates of solvent and water are controlled via a feedback loop (PID-based algorithm) using software (Elveflow, ESI 3.07.01), and the droplet formation process in the microfluidic chip is monitored using an inverted optical microscope equipped with a high-speed imaging system (PreciGenome, PG-HSV-M, 32GB, 5x and 20x objectives). The polymer droplets collected in the glass reservoir are stirred and dried at room temperature for 0.2-6 hours at a relative humidity of 20-60% until the solution becomes clear. After evaporation, the synthetic spikes (polymer particles) are dispersed in DI water and rinsed several times by repeated centrifugation at 10,000-12,000 rpm for 10 minutes and removal of the supernatant to remove residual surfactants. After removing the supernatant, the precipitate of the synthetic needle can be redispersed in a liquid medium or used in powder form.

[0084] Example 2 - Preparation and Geometry Related Parameters Various parameters can be adjusted in the synthetic needle preparation system to customize the geometry and throughput. These parameters are listed in Table 2, and detailed information is described below.

[0085] Table 2. List of preparation parameters and related geometric / manufacturing variables for manufacturing synthetic spiky bodies.

[0086] Synthetic puncture body pore size ( ）：The pore size of the synthetic needle ( The mass fraction of the hydrophilic polymer in the oil-in-water system can be adjusted. HP ) and the number-average molecular weight of the polymer ( n This is determined by [the specific process described]. Specifically, during interfacial instability processes, a larger hydrophilic fraction induces a smaller fluctuation curvature, resulting in larger pores after solvent evaporation, as shown in Figures 3A-3B. (Figure 3B shows that when molecular weights are similar, a larger [hydrophilic fraction] induces a smaller fluctuation curvature, resulting in larger pores.) HP The pore size of the polymer increases. (Typically, for PS-b-P4VP block copolymers,) HP The open porosity can be obtained in the range of 0.1–0.25. Furthermore, the molecular weight of the polymer determines the entire length scale of the synthesized spike particles, including the pore size. Generally, for polymers with larger molecular weights, the length of the polymer molecules increases, and the diameter increases with the diameter of the permeated water droplets. Figures 3A and 3C illustrate similar patterns. HP The pore size of the synthetic needles is increased.

[0087] Synthetic spiky wall thickness ( w ）： Synthetic spiky wall thickness ( w ( ) refers to the minimum distance between the edges of two adjacent pores on the surface of the puncture body, which can be determined by molecular weight ( n The wall thickness is adjusted accordingly. Specifically, the wall thickness is proportional to the size of the polymer molecules, as shown in Table 1 and Figure 3C. For PS-b-P4VP block copolymers, the wall thickness varies in the range of 23.85-121.25 nm.

[0088] Synthetic puncture porosity ( ）： Porosity of synthetic needles ( The ratio of aperture to wall thickness () / w This is related to the fact that, specifically, for particles with the same wall thickness, porosity increases with increasing pore size. For example, from PS... 45k -b-P4VP 5.5k and PS 48k -b-P4VP 11k The synthesized thorns had similar molecular weights and consequently wall thicknesses, but exhibited different pore sizes and porosities, as shown in Table 1 and Figures 3A-3B.

[0089] Particle size ( ）： Particle size of synthetic spikes ( The diameter of the synthesized spike particles is determined by the size and number of polymer molecules contained in the solvent droplets. Therefore, the diameter of the synthesized spike particles depends on the following parameters: (1) the polymer concentration in the solvent ( p (2) Solvent flow rate ( s ) and water flow rate ( w ), and (3) the molecular weight of the polymer ( n The number of polymer molecules in a solvent droplet is directly proportional to the final particle size after solvent evaporation; therefore, a higher polymer concentration in the solvent droplet induces a larger particle size. Figures 6A-6B Similarly, for the same polymer at the same concentration in a solvent, larger solvent droplets contain more polymer molecules and can result in larger particles. Figures 7A-7B In this case, the particle size of the synthesized spikes can be estimated from the solvent droplet size using the following equation: in, It is the volume of the synthetic spike particles. s It is the density of the solvent. s It is the volume of the solvent droplet. p This is the polymer concentration, expressed as % (w / w). It is the solid fraction of the synthetic spike, and p This is the density of the polymer. Here, the solids fraction can be assumed to be in the range of 0.1 (90% porosity) to 1 (zero porosity). In the equation, it contains 0.04% (w / w) PS. 48k -b-P4VP 11k The diameter of the toluene droplets was reduced from 5.32 μm to 520 nm, resulting in the synthesis of spikes, thus assuming a solids fraction of 0.35, which matches the experimental results shown in Figure 7B very well. Furthermore, the solvent droplet diameter ( ) can be achieved through solvents in microfluidic systems ( s ) and water ( w Adjust the flow rate, such as Figure 22 As shown. Typically, w and sThe higher the ratio, the smaller the droplets obtained. Furthermore, the size of the polymer molecules increases with... n Change, and therefore and n Proportional ( Figures 8A-8C To obtain submicron-sized synthetic spikes, a polymer concentration of 0.02–0.2% (w / w) is used for solvent droplet diameters of 4–12 μm.

[0090] Hole depth (h): Hole depth ( h () refers to the depth of the pores at the surface of the synthetic piercing, and can be 0- Within the range, This refers to the diameter of the synthetic spike particles. In terms of pore morphology, closed pores can be characterized as... h Approaching 0, while when h It is approximately 0.5 When the pore depth is similar to the particle size, it can indicate a clear opening. h ≈ This allows for the formation of a sac-like structure (Figure 4L) instead of a spherical, spiky structure. The pore depth is influenced by various factors, such as polymer concentration, solvent droplet evaporation rate, surfactant concentration, and the mass fraction of the hydrophilic polymer. Specifically, low polymer concentrations and rapid evaporation rates reduce the pore depth. Figures 9A-9C , Figures 10A-10B Therefore, submicron-sized spiky-like structures were obtained. h ≈ 0.5 The key is to reduce the evaporation rate, which requires using small solvent droplets (4-12 μm in diameter) and low polymer concentrations. Here, the evaporation rate is adjusted by adding an aqueous solvent emulsion to the tank that collects the solvent droplets forming the spikes. If necessary, the tank can be covered with a Parafilm perforated to the size of the outlet pipe to further reduce the evaporation rate. Furthermore, h At low concentrations of surfactant, the surface tension is close to zero, and these low concentrations induce a smaller decrease in surface tension at the interface between the solvent droplets and the aqueous medium (Ku et al., "Particles with tunable porosity and morphology by controlling interfacial instability in block copolymer emulsions"). ACS Nano 10:5243-5251, 2016). Here, tests were conducted using a fixed concentration of surfactant (0.4% (w / w)) to demonstrate the effect of evaporation rate and polymer concentration on pore depth.

[0091] Throughput (TH): Compared to existing methods for manufacturing synthetic spikes, the use of microfluidics offers significant advantages in terms of production rate. In this method, the production rate of synthetic spikes is directly related to the throughput (or droplet rate) of polymer-containing solvent droplets generated in the microfluidic system. The throughput can be calculated as follows: in s It is the solvent flow rate, and s This refers to the volume of solvent droplets generated in the system. Based on estimates and experimental results using a high-speed imaging system, the throughput of the system (a single droplet generator with a 10 μm nozzle connected to a pressure regulator with a maximum pressure of 2 bar) ranges from 6,500 to 120,000 droplets / second. Figure 22 ).

[0092] Example 3 - Morphological Transformation of Pore Structure Most natural spines exhibit a buckyball-like structure characterized by pentagonal and hexagonal surface pores. While these buckyball-like spines are dominant, some species display circular or near-circular pores. Interestingly, synthetic spines exhibit a variety of pore morphologies, including circular, polygonal, and amorphous shapes, such as… Figure 11A-11C As shown. To simulate the different pore morphologies observed in natural spines and to understand how morphological transitions occur in synthetic spines, a study was conducted investigating the surface energy of the emulsion system.

[0093] Surface energy and critical interfacial tension: Interfacial tension is the energy required per unit area to increase the surface area of ​​the interface between two immiscible fluids. Typically, the addition of surfactants or amphiphilic polymers reduces interfacial tension because these molecules adsorb at the interface. The composition of the amphiphilic polymer also affects interfacial tension; generally, in systems consisting of water and water-immiscible fluids, an increase in the hydrophilic portion leads to a more significant reduction in interfacial tension [71, 79].

[0094] In this system, the pores of the synthetic spikes are caused by water permeating into a solvent droplet containing an amphiphilic block copolymer. After permeation, the water droplet becomes spherical to minimize its surface energy. As the solvent droplet evaporates, its volume decreases, causing the polymer to solidify and resulting in a close packing of the permeated water droplets. During this process, if the interfacial tension is low enough, the permeated water droplet may deform, thereby increasing its surface area. Specifically, when the interfacial tension is high, the energy to minimize the surface area is large, and the water droplet within the solvent droplet tends to maintain its spherical shape. Therefore, the final pore after complete solvent evaporation tends to be circular because spherical shape provides the minimum surface energy for a given volume. Conversely, when the interfacial tension is low, the energy driving the minimization of the surface area is weaker. Therefore, the water droplets deform as they pack together, taking on various shapes, resulting in polygonal or irregularly shaped pores

[80] .

[0095] To determine the critical interfacial tension for the transition of the aperture shape from spherical to polygonal or amorphous ( The study considered the energy contributions of interfacial tension and morphological transformation. The key idea is that a transformation occurs when the surface energy difference between the spherical and deformable shapes becomes negligible. in This is the difference in surface energy between a deformed water droplet and a spherical water droplet. The surface energy of a spherical water droplet is given by the following formula: in and These are the reference interfacial tension and surface area of ​​the spherical droplet, respectively. If the spherical droplet increases its surface area... If the droplet is deformed into a polygon or amorphous shape, then the interfacial energy of the deformed droplet can be written as follows: in It is the critical interfacial tension for the deformation of a spherical droplet, and It is the surface area of ​​the deformable droplet. Therefore, It can be represented as: This equation allows for the transformation of the aperture shape from spherical to polygonal or amorphous. Specifically, for The system is beneficial for the deformation of the hole shape, while for Spherical holes are preferred.

[0096] Morphological transformation within the pores of synthetic spiky:To investigate the morphological transformation of pores in synthetic spikes, the interfacial tension of toluene-containing PS-b-P4VP was measured using the inverted pendant drop tensiometric method in the presence of a 0.4 wt% sodium dodecyl sulfate (SDS) aqueous solution. Figure 15 As a reference for the model system, the interfacial tension of pure toluene was measured under the same conditions. To investigate the effect of amphiphilic polymer properties on interfacial tension, different compositions and molecular weights of PS-b-P4VP were tested. The number of PS-b-P4VP molecules dissolved in toluene remained constant at 0.03 mM.

[0097] To estimate the morphological transformation of surface holes (from circular to polygonal holes, and from circular to amorphous holes) The study modeled circular pores as hemispherical shapes, polygonal pores as hexagonal prisms, and amorphous pores as isosceles triangular prisms. To determine their geometry, it was assumed that these structures had the same projected area and volume, since the volume of the infiltrating droplets is conserved during deformation. Figure 12 Examples of three different surface morphologies are shown, and Figures 13A-13B The internal hole morphology is shown in the figure.

[0098] The study models circular holes as hemispherical droplets, with the circular base facing the external aqueous phase (indicated by the blue-filled area) and the remaining spherical surface exposed to the toluene medium (represented by the yellow-filled area). Polygonal holes are hexagonal prisms, with one hexagonal face facing the aqueous medium and the remaining face in contact with toluene. For amorphous holes, the study assumes an isosceles triangular prism configuration. To determine the geometry, the study maintains the same projected area and volume, assuming that the volume of the permeating droplet remains constant during deformation.

[0099] To estimate the formation of polygonal holes The study calculated the surface area of ​​two different structures facing the toluene medium. The ratio of (the yellow-filled area). Here, the base radius of the hemisphere is defined as... And the side length and height of the hexagonal prism are respectively expressed as and By assuming the same projected area and constant volume, and use It is expressed as follows: The study determined The reference interfacial tension is 3.53 mN / m, compared to 4.23 mN / m. The interfacial tension between water containing 0.4 wt% SDS and toluene without amphiphilic polymers.

[0100] For the sake of simplicity, the study models amorphous porous structures as having an aspect ratio of... n (i.e., in the above diagram) b and c Based on observations, isosceles triangular prisms (ratio of which) typically exhibit elongated triangular surface pores, where particles with lower amorphous properties generally show these characteristics. Figures 14A-14B Similar to previous estimates, k The calculation can be performed as follows: Use aspect ratio n = 2 is used to represent the elongated shape of a hole with a low degree of amorphousness, and the study calculated that It is 2.90 mN / m. It should be noted that the degree of amorphousness increases with... n It increases with the improvement, and leads to reduce.

[0101] According to estimates, the amount required to form a polygonal hole The strength is 3.53 mN / m, while the amorphous hole is modeled by an isosceles triangular prism with an aspect ratio of 2. The value is 2.9 mN / m. These values ​​match well with the observed transition point and the measured interfacial tension. Figure 15 It should be noted that when pores are uniformly structured on the particle surface, well-defined hexagonal or pentagonal pores are formed. This uniformity allows the infiltrated water droplets to form a honeycomb-like arrangement when they are tightly packed together [60, 79, 81-83], in which the overall geometry is similar to that found in natural spiky bodies, exhibiting a buckyball geometry.

[0102] Example 4 - Application Monodisperse synthetic spikes with customizable morphologies have potential applications in various fields such as functional coatings, pigments, and optical feature management.

[0103] Liquid-repellent and hydrophobic coating:To demonstrate the observed increase in hydrophobicity in its natural counterpart, the surface of synthetic spike particles with hydrophilic polymers exposed on the particle surface can be modified by silanization. Surface functionalization can be accomplished via liquid-phase or gas-phase silanization for synthetic spikes dispersed in liquid media (e.g., water, ethanol, and isopropanol) or deposited on various substrates (e.g., Si wafers and microscope slides). A variety of silanes can be used, including alkoxysilanes such as monoalkoxysilanes, e.g., trimethylmethoxysilane; dialkoxysilanes, e.g., dialkoxy; dialkylsilanes, e.g., dimethyldimethoxysilane; dialkoxy, fluoroalkyl, or perfluorosilanes; trialkoxysilanes, e.g., 1H,1H,2H,2H-perfluorodecyltriethoxysilane; alkyl, chlorosilanes, e.g., octyldimethylchlorosilane, etc. The alkoxy group of such silanes can be C 1-4 Alkyl groups, such as methoxy (-OCH3) and ethoxy (-OCH2CH3), and alkyl groups can have various chain lengths, such as C10 and C20. 1-30 Alkyl groups. As a demonstration, this was achieved by using dimethyldimethoxysilane to react with 0.2% (w / w) PS. 109k -b-P4VP 27k The prepared synthetic spikes were chemically functionalized, resulting in a pore size of approximately 230 μm, a particle size of approximately 900 nm, and a solids fraction of approximately 0.3%. Specifically, the synthetic spikes were rinsed with a silane solution containing 9% dimethyldimethoxysilane, 0.9% sulfuric acid, and 90.1% isopropanol for at least 30 minutes at room temperature or in an oven at 75°C. After solvent evaporation, the synthetic spikes were chemically functionalized with a grafted silicone layer. Following surface treatment, the average water contact angle increased from 5° (untreated synthetic spikes) to 124° (chemically functionalized spikes), demonstrating a significant enhancement in hydrophobicity.

[0104] Anti-reflective coating: Previous studies have demonstrated that synthetic spikes possess antireflective properties, significantly reducing specular reflection at ultraviolet to near-infrared (UV to near-IR) wavelengths [16-18]. A key advantage of synthetic spikes is their angle-independent antireflective capability, making them promising for a wide range of optical applications [16, 42]. However, the low production rate and complex manufacturing process of synthetic spikes limit their applications.

[0105] To overcome these limitations, an experiment was conducted that fabricated individual three-dimensional synthetic spikes. The system used to produce the synthetic spikes enabled the mass production of synthetic spikes with consistent size and shape, thus allowing for a broader exploration of their optical properties.

[0106] To demonstrate the antireflective properties of these synthetic spikes, three samples were prepared: a gold mirror as a total reflection control, a gold-coated synthetic spike, and an uncoated synthetic spike (both with a diameter of approximately 1 μm). For the coated synthetic spike, gold was sputtered in 30 nm layers to enhance the plasma effect [16, 91, 92]. Figures 16A-16D As shown, the specular reflectance was measured experimentally, and the reduction in reflectance spectra in the wavelength range of 250 nm to 2200 nm was calculated for both coated and uncoated synthetic spikes. The results indicate a significant reduction in reflectance, with the uncoated synthetic spikes showing a reduction of 89–98%, while the gold-coated spikes exhibited an even greater reduction, achieving reflectance values ​​between 94.5% and 98.6%. These findings highlight the potential of synthetic spikes in advanced antireflective coatings, particularly in applications requiring broadband reflection suppression across a wide wavelength range.

[0107] White pigment: The aggregates of the synthetic spike particles exhibited a bright whiteness and can be considered a potential alternative to titanium dioxide (TiO2), a commercial white pigment used in sunscreens, food, and paints as a whitening dye. To demonstrate the bright whiteness (referring to the bright whiteness produced by the broadband scattering of the material's non-periodic structure in the visible spectrum), the diffuse reflectance spectrum of the synthetic spikes was compared with that of TiO2. Here, the synthetic spikes consist of 0.2% (w / w) PS... 109k -b-P4VP 27k The synthetic spikes, produced, have a pore size of approximately 230 μm and a particle size of approximately 900 nm. For example... Figures 17A-17B As shown, the reflectance spectrum of the synthetic spikes exhibits a considerable degree of reflectance in the visible wavelength range, and the optical images of the deposits confirm the whiteness of their appearance.

[0108] UV blocking agent: Due to the high scattering properties of the synthetic stinger, it can be used as a UV blocker, as a substitute for TiO2, a commonly used UV blocker in sunscreens and cosmetics. To demonstrate its UV blocking ability, a mixture of 0.2% (w / w) PS was prepared. 109k -b-P4VP 27k The prepared synthetic spikes, having a pore size of approximately 230 μm and a particle size of approximately 900 nm, were then dispersed in decamethylcyclopentasiloxane, a silicone oil commonly used in cosmetics as a moisturizer. The solution was then deposited onto a UV-transparent quartz microscope slide approximately 0.2 mm thick, and the transmittance of the deposit was measured. Figure 18 As shown, the synthetic spikes blocked approximately 99% of UV light.

[0109] Scattering / absorbing plumes for directional visibility The synthetic spikes exhibited interesting optical properties [16-18, 23, 41-43, 46, 90], including both light scattering and absorption [16, 18], suggesting their potential to act as efficient scattering plumes. To investigate their performance in directional vision, an experiment was conducted in which monodisperse synthetic spikes were compared with nonporous spheres (both composed of PS-b-P4VP) (Figs. 19C-19D).

[0110] To demonstrate this, the absorber and scatterer were dispersed in separate fluid media contained in cuvettes, thus simulating the behavior of two parallel atmospheric plumes (Figures 19A-19B). Carbon black was used as the absorber and dispersed in isopropanol (IPA) at a concentration of 0.062 wt%. Two different masking agents (synthetic spikes and non-porous particles) were dispersed at 2 × 10⁻⁶ ppm. 9 An initial concentration of particles / mL was dispersed in water. The concentration of the absorbing plume was kept constant, while the concentration of the scattering plume was varied through successive dilutions to assess its effect on contrast. A 1951 USAF resolution target was printed and used as the target image, with white light illuminating the entire setup to simulate sunlight. Visibility was captured from each side (absorbing and scattering sides) using a digital camera equipped with a macro lens. The image contrast ( ) is defined as ,in and The radiance values ​​are the target and its background, respectively. Radiance was measured using ImageJ, with averages obtained at five different regions in each image. Image contrast observed from the absorption and scattering plume sides is expressed as follows: C ab and C sc .

[0111] As a result, the synthetic spikes exhibited a wider dynamic range in terms of concentration, with the most significant increase observed at 89% (1.8 × 10⁻⁶) of the initial scatterer particle concentration. 9 From 14% (particles / mL) to 14% (2.8 × 10⁻⁶). 8 Directional visibility was observed within the range of particles / mL (Fig. 20A, Fig. 20C-20D). Specifically, at the initial scatterer particle concentration (100%), visibility was blocked on both the absorber and scatterer sides. Directional visibility was first observed at 89% of the initial concentration, while below 14%, clear visibility was observed on both sides, indicating loss of directional visibility. Based on these observations, the threshold for achieving directional visibility can be defined as a contrast ratio between the absorber and scatterer sides exceeding 2 (i.e., ...). C ab / Csc >2) points (Fig. 20D). In contrast, the non-porous sphere exhibits a narrower dynamic range, with only 14% (2.6 × 10) points. 7 (particles / mL) and 3% (2.8 × 10⁻⁶) 8 Directional visibility was achieved between particles per mL, as shown in Figures 20B-20D.

[0112] It is speculated that the enhanced directional visibility of synthetic spikes compared to non-porous spheres is due to the spikes' porous structure, which not only scatters light but also increases transparency. While scattering is crucial for directional visibility, the transmittance of the plume also significantly affects visibility, as the target must remain visible. The cavities of the spikes may produce higher transmittance compared to non-porous particles, which could explain the wider effective concentration range for achieving directional visibility.

[0113] This experiment demonstrates the significant potential of synthetic spikes as scattering masking agents for achieving directional visibility, offering a wider dynamic concentration range compared to non-porous spherical particles. This wider range is particularly advantageous in atmospheric environments, where particle concentrations can dynamically vary due to diffusion, convection, and gravitational settling. Using synthetic spikes as masking agents allows for longer durations of directional visual effects. Furthermore, the porous nature of synthetic spikes results in lower particle density compared to non-porous particles, further extending their settling time. For example, when comparing the settling time of synthetic spikes with a diameter of 1 μm and non-porous particles over a distance of 1 meter, the settling time of the synthetic spikes was 23.4 hours, while that of the non-porous particles was only 8.4 hours. Figure 15 When synthetic spikes are used as masking agents, this extended settling time allows for a longer duration of the directional visual effect.

[0114] Fluorescent particle tracer: To demonstrate the ability of the synthesized spikes as fluorescent particle tracers, pyrene, a water-insoluble blue fluorescent dye, was dissolved in a polymer-containing solvent using a magnetic stirrer. Here, 0.04% (w / w) PS was used. 109k -b-P4VP 27k And 0.02% (w / w) of pyrene. The solvent was then connected to a microfluidic system to produce solvent droplets containing the polymer and pyrene. After collecting and drying the solvent droplets, synthetic pyrene-encapsulated spikes were formed. The particles were rinsed by repeating the same procedure used to prepare the synthetic spikes, and imaged using an optical microscope (Zeiss, Axio Imager 2). Figures 21A-21B ).

[0115] The following patents, applications and publications listed below and throughout this document are hereby incorporated herein by reference in their entirety.

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Claims

1. A method for forming a synthetic brochosome, the method comprising: (i) a polymer solution containing a solvent and an amphiphilic polymer is combined with (ii) an external fluid that is immiscible with the solvent, thereby forming droplets of the polymer solution in the external fluid, wherein the amphiphilic polymer has a hydrophobic polymer component and a hydrophilic polymer component. The external fluid and the solvent are removed from the droplet, thereby providing a synthetic stinger.

2. The method of claim 1, wherein the polymer solution and the external fluid are combined in a microfluidic device.

3. The method of claim 1, wherein the solvent and the external fluid are removed from the droplets by evaporation, freeze-drying, centrifugation, or any combination thereof.

4. The method of claim 1, wherein the synthetic needle is rinsed, dried, suspended in a liquid medium, or any combination thereof.

5. The method of claim 1, wherein the method comprises forming an oil-in-water emulsion with the solvent and the external fluid; The solvent is at a concentration of about 0% v / v to about 99% v / v; and The polymer solution is added to the emulsion.

6. The method of claim 5, wherein the hydrophilic polymer is present in a mass fraction of about 0.05 to about 0.

45.

7. The method of claim 1, wherein the method comprises forming a water-in-oil emulsion with the solvent and the external fluid; The solvent is at a concentration of about 0% v / v to about 99% v / v; and The polymer solution is added to the emulsion.

8. The method of claim 7, wherein the hydrophobic polymer is present in a mass fraction of about 0.05 to about 0.

45.

9. The method according to claim 1, wherein the solvent is toluene, acetone, pentane, hexane, heptane, octane, isooctane, nonane, decane, undecane, dodecane, hexadecane, cyclohexane, dimethyl carbonate, chloroform, dichloromethane, benzene, silicone oil, tetrahydrofuran, xylene, trichloroethylene, methyl tert-butyl ether (MTBE), methyl ethyl ketone (MEK), methanol, ethanol, isopropanol, butanol, hexanol, octanol dimethylformamide, dichloroethane, carbon tetrachloride, water, or any combination thereof.

10. The method of claim 1, wherein the external fluid is water.

11. The method of claim 1, wherein the external fluid further comprises a surfactant.

12. The method of claim 11, wherein the surfactant is present in the external fluid in the range of about 0.05% w / w to about 0.8% w / w.

13. The method according to claim 1, wherein the amphiphilic polymer is poly(styrene)-b-poly(4-vinylpyridine), poly(styrene)-b-poly(acrylic acid), poly(styrene)-b-poly(vinyl alcohol), poly(D-lactide)-polyethylene glycol methyl ether, polyethylene glycol-poly(lactide-co-lactide), poly(D,L-lactide), polylactide-polyethylene glycol-COOH, poly(ethylene glycol) methyl ether-block-poly(D,L-lactide), methoxy poly(ethylene glycol) )-b-poly(caprolactone), carboxylic acid poly(ethylene glycol)-block-poly(lactide-co-lactide), methoxy poly(ethylene glycol)-b-poly(lactide-co-lactide), methoxy (polyethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(D,L-lactide), amphiphilic bottle brush block copolymers, amphiphilic copolymers based on PolyPEG-stearic acid, amphiphilic proteins, or any combination thereof.

14. The method of claim 1, wherein the amphiphilic polymer has a number-average molecular weight of about 1 kg / mol to about 1000 kg / mol.

15. The method of claim 1, wherein the synthetic spike has a particle size of about 100 nm to about 20 µm.

16. The method of claim 1, wherein the synthetic thorn has a pore size of about 20 nm to about 5 µm.

17. The method of claim 1, wherein the synthetic thorn has a pore depth of about 10 nm to about 5 µm.

18. The method of claim 1, wherein the synthetic thorn has a porosity of about 0.1 to 0.

9.

19. The method of claim 1, wherein the synthetic spike has a wall thickness of about 10 nm to about 2 µm.

20. A synthetic spiky body comprising an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, wherein the hydrophilic polymer component is present in a mass fraction of about 0.05 to about 0.

45.

21. The synthetic spike according to claim 20, wherein the amphiphilic polymer is poly(styrene)-b-poly(4-vinylpyridine), poly(styrene)-b-poly(acrylic acid), poly(styrene)-b-poly(vinyl alcohol), poly(D-lactide)-polyethylene glycol methyl ether, polyethylene glycol-poly(lactide-co-lactide), poly(D,L-lactide), polylactide-polyethylene glycol-COOH, poly(ethylene glycol) methyl ether-block-poly(D,L-lactide), methoxy poly(ethylene glycol) (Alcohol)-b-poly(caprolactone), carboxylic acid poly(ethylene glycol)-block-poly(lactide-co-glycolic acid), methoxy poly(ethylene glycol)-b-poly(lactide-co-glycolic acid), methoxy (polyethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(D,L-lactide), amphiphilic bottle brush block copolymers, amphiphilic copolymers based on PolyPEG-stearic acid, amphiphilic proteins, or any combination thereof.

22. The synthetic spike according to claim 20, wherein the hydrophobic polymer component is present in a mass fraction of about 0.95 to about 0.

55.

23. The synthetic spiky body according to claim 20, wherein the amphiphilic polymer has a number-average molecular weight of about 1 kg / mol to about 1000 kg / mol.

24. The synthetic spike of claim 20, wherein the synthetic spike has a particle size of about 100 nm to about 20 µm.

25. The synthetic needle of claim 20, wherein the synthetic needle has a pore size of about 20 nm to about 5 µm.

26. The synthetic needle of claim 20, wherein the synthetic needle has a pore depth of about 10 nm to about 5 µm.

27. The synthetic needle of claim 20, wherein the synthetic needle has a porosity of about 0.1 to 0.

9.

28. The synthetic needle of claim 20, wherein the synthetic needle has a wall thickness of about 10 µm to about 2 µm.

29. A composition comprising the synthetic spiky body and carrier according to claim 20.

30. The composition of claim 29, wherein the composition is a coating, pigment, powder, or detergent.

31. A synthetic spiky body comprising an amphiphilic polymer having a hydrophobic polymer component and a hydrophilic polymer component, wherein the hydrophobic polymer component is present in a mass fraction of about 0.05 to about 0.

45.

32. The synthetic spike according to claim 31, wherein the amphiphilic polymer is poly(styrene)-b-poly(4-vinylpyridine), poly(styrene)-b-poly(acrylic acid), poly(styrene)-b-poly(vinyl alcohol), poly(D-lactide)-polyethylene glycol methyl ether, polyethylene glycol-poly(lactide-co-lactide), poly(D,L-lactide), polylactide-polyethylene glycol-COOH, poly(ethylene glycol) methyl ether-block-poly(D,L-lactide), methoxy poly(ethylene glycol) (Alcohol)-b-poly(caprolactone), carboxylic acid poly(ethylene glycol)-block-poly(lactide-co-glycolic acid), methoxy poly(ethylene glycol)-b-poly(lactide-co-glycolic acid), methoxy (polyethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(L-lactide), methoxy poly(ethylene glycol)-b-poly(D,L-lactide), amphiphilic bottle brush block copolymers, amphiphilic copolymers based on PolyPEG-stearic acid, amphiphilic proteins, or any combination thereof.

33. The synthetic spiky body according to claim 31, wherein the hydrophilic polymer component is present in a mass fraction of about 0.95 to about 0.

55.

34. The synthetic spiky body according to claim 31, wherein the amphiphilic polymer has a number-average molecular weight of about 1 kg / mol to about 1000 kg / mol.

35. The synthetic spike according to claim 31, wherein the synthetic spike has a particle size of about 100 nm to about 20 µm.

36. The synthetic needle of claim 31, wherein the synthetic needle has a pore size of about 20 nm to about 5 µm.

37. The synthetic needle of claim 31, wherein the synthetic needle has a pore depth of about 10 nm to about 5 µm.

38. The synthetic needle of claim 31, wherein the synthetic needle has a porosity of about 0.1 to 0.

9.

39. The synthetic thorn of claim 31, wherein the synthetic thorn has a wall thickness of about 10 nm to about 2 µm.

40. A composition comprising the synthetic spiky body and carrier according to claim 31.

41. The composition of claim 40, wherein the composition is a coating, pigment, powder, or detergent.

Images