Optical filtering materials and methods for biomaterial integration - Patents.com

Abstract

1. A composition for light filtering, the composition comprising: a base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak light absorption value in a range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having a spectral peak that is at least partially quenched by filtering a spectral curve of the nanoparticles; 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 nanoparticles.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 17 / 661,110, 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] Selective light blocking is desirable for a wide variety of soft biomaterials, including contact lenses. For safety, therapeutic, and cosmetic reasons, there is a great need for biomaterials that can block specific ranges of wavelengths.

[0004] Currently available contact lenses adjust the curvature and / or refractive index of the eye to improve focusing. However, such commercially available contact lenses do not improve other aspects of vision, such as color perception. Impaired color perception / discrimination can significantly affect a person's quality of life. Traditionally, contact lens gels have been used for specific light blocking. However, although specific light blocking using contact lens gels can have beneficial results, the resulting color intensity of contact lens gels is often bright (due to the use of fluorescent dyes) and is generally not cosmetically desirable.

[0005] Furthermore, while approaches to selective light blocking exist, there are no solutions that can be uniformly dispersed within biomaterials, can be tuned to different wavelengths of interest without changing the fundamental mechanism, can block light with minimal fluorescence, can withstand long-term storage and autoclaving, and / or can be readily adopted commercially.

[0006] A method describing the dispersion of metal nanoparticles for optical filtering in sunglasses is described in US 2007 / 0298242 A1. Gold nanoparticles or dyes are dispersed in a polymer matrix, and the composite either acts as the lens itself or is used as a coating on one or both sides of the lens. US 2007 / 0298242 A1 does not disclose information regarding the immobilization of light blocking materials within a polymer matrix, which is necessary for the integration of light blocking materials into soft materials.

[0007] 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 within the hydrogel contact lens during the extraction and / or hydration steps. The method described may be convertible to gold nanoparticles and / or dyes, but the patent does not disclose information regarding light blocking materials or chemical embedding of these materials into 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.

[0008] A method for imparting specific light-blocking capabilities to contact lenses using rhodamine dyes 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 tinted contact lenses for treating color vision deficiencies. Similar to US 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 other processes. The lack of integration of the light-blocking material into the contact lens results in depletion of the dye in the contact lens after incubation in phosphate-buffered saline (PBS). This publication also does not demonstrate that different wavelengths can be targeted using the same method. Variations in the dye required to generate light-blocking materials at different wavelengths may affect passive incorporation into biomaterials. Summary of the Invention [Problem to be solved by the invention]

[0009] However, improvements over the methods and materials of the prior art are needed. [Means for solving the problem]

[0010] Disclosed herein are systems, compositions, and methods for light filtering.

[0011] 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 650 nm to about 800 nm, a chemical dye dispersed in the base material, the chemical dye having an emission peak that at least partially overlaps with the peak optical absorption of the plurality of gold nanoparticles, and a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

[0012] One general embodiment includes a composition for light filtering, the composition also including a base material, a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak light absorption value in a range of about 650 nm to about 800 nm, a chemical dye dispersed in the base material, the chemical dye having an abortion peak in a range of about 530 nm to about 560 nm, and a nanoparticle coating material disposed on at least a portion of the plurality of nanoparticles.

[0013] 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]

[0014] The following drawings illustrate generally, by way of example, but not by way of limitation, various examples contemplated in the present disclosure. [Figure 1A] 1 illustrates a surface modification strategy according to an embodiment of the present disclosure. [Figure 1B] 1 illustrates a surface modification strategy according to an embodiment of the present disclosure. [Figure 1C] 1 illustrates a surface modification strategy according to an embodiment of the present disclosure. [Figure 2A] 1 illustrates the selection of gold nanostars as a platform for light blocking materials according to embodiments of the present disclosure. [Figure 2B] 1 illustrates the selection of gold nanostars as a platform for light blocking materials according to embodiments of the present disclosure. [Diagram 3]1 shows the Ultraviolet-Visible (UV-Vis) spectra of nanoparticles synthesized with different amounts of seeds. [Figure 4A] 1 shows the effect of seeding on nanoparticle morphology. [Figure 4B] 1 shows the effect of seeding on nanoparticle morphology. [Figure 4C] 1 shows the effect of seeding on nanoparticle morphology. [Figure 4D] 1 shows the effect of seeding on nanoparticle morphology. [Figure 5A] 1 shows a spectrum of a dye-nanoparticle (dye-NP) light blocker in solution according to an embodiment of the present disclosure. [Figure 5B] 1 shows a spectrum of a dye-nanoparticle (dye-NP) light blocker in solution according to an embodiment of the present disclosure. [Figure 6] 1 shows the color profile of a dye-NP light blocker compared to existing methods according to embodiments of the present disclosure. [Figure 7] 1 shows the ultraviolet-visible (UV-Vis) spectrum of a Rhodamine 6G nanoparticle optical filter. [Figure 8] 1 shows the ultraviolet-visible (UV-Vis) spectrum of a Rhodamine B nanoparticle optical filter. [Figure 9] 1 shows the ultraviolet-visible (UV-Vis) spectrum of a tetramethylrhodamine (TRITC) nanoparticle optical filter. [Figure 10] 1 shows the ultraviolet-visible (UV-Vis) spectrum of a 5-carboxy-tetramethylrhodamine nanoparticle optical filter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Filtering (e.g., blocking) a specific range of light can help improve color perception. As a non-limiting example, filtering light in the region between the red and green cones can help improve contrast and color perception for people with red-green color vision deficiency, as shown in FIG. 1A. Organic dyes are well adapted to block a very narrow range of the visible light spectrum. However, they suffer from leakage over time (because they are not trapped within the contact lens matrix) and poor patient compatibility (because they are fluorescent and very brightly colored). Because individual needs can vary dramatically, the mechanism by which specific light filtering is achieved should be modular and adjustable for different wavelengths.

[0016] The present disclosure relates to nanoparticles. Such nanoparticles may exhibit tunable photophysical properties. By exhibiting tunable photophysical properties, the nanoparticles may absorb, scatter, and / or extinguish light of specific wavelengths. Such wavelengths may be anywhere in the visible spectrum. The nanoparticles may be integrated as tunable optical filters in optically transparent substrates to produce devices. Such devices may include ophthalmic devices, although other devices are possible. As a non-limiting example, the ophthalmic device may further include a contact lens. The integration of light filtering materials into contact lenses may be required so that such materials are stable and retained for long periods of time. As a result, there is a need to develop light filtering materials that have specificity for certain wavelengths, reduced color intensity compared to conventional light filtering contact lens gels, and long-term stability and retention in gel-like medical devices.

[0017] The present disclosure provides a light blocking material and method for biomaterial integration. The present disclosure addresses a critical gap in current light blocking technology and materials for contact lenses. The method of providing a light blocking material for biomaterial integration includes selecting nanoparticles. Such nanoparticles may include gold nanoparticles. Such gold nanoparticles may further include a specific shape. The present disclosure further relates to chemical dyes (e.g., dyes used in food preparation or coloring). The present disclosure further relates to stabilization mechanisms. Such stabilization mechanisms may include nanoparticle coating materials configured to stabilize selected nanoparticles. The present disclosure relates to binding of nanoparticles to chemical dyes. Such binding may include chemical bonds. The combination of nanoparticles and chemical dyes allows for specific light filtering with less intense colors. The decrease in color intensity of the material may be due to the fluorescence of the chemical dye being quenched by the nanoparticles. The chemical dye may be in close proximity to the nanoparticles to achieve fluorescence quenching. Fluorescence quenching is known in the art and may occur due to the gold nanoparticles absorbing light at wavelengths sufficiently longer than the initial light emitted by the dye. Thus, the method may include using a crosslinker to chemically bond the nanoparticles to the chemical dye. A non-limiting example of the crosslinker may include a short chain thiol. The present disclosure further relates to a stabilization mechanism. The stabilization mechanism may improve the stabilization quality relative to the chemical dye. The stabilization mechanism may partially replace the chemical dye conjugated to the nanoparticle. The stabilization mechanism may include a long chain polymer. The long chain polymer may stabilize the nanoparticles through increased steric hindrance. The stabilization mechanism may also be biocompatible and compatible with the gel material. Such compatibility may allow homogeneous dispersion of the nanoparticles in the biomaterial. The stabilization mechanism may also intervene in the chains of the biomaterial through chain entanglement, fixing the nanoparticles in the gel for an extended period of time. Additional capabilities may be used, such as different dyes (or combinations thereof) that target different wavelengths of interest. Additional shapes of gold nanoparticles that quench the fluorescence of various dyes may be used.

[0018] The present disclosure relates to nanoparticles, such as metal nanoparticles, more specifically, for example, gold nanoparticles. Reference to gold nanoparticles may apply to other nanoparticles, including metal nanoparticles. The nanoparticles may be gold nanoparticles. The gold nanoparticles may be star-shaped gold nanoparticles that block light in the range of about 650 nm up to about 800 nm. Such an absorbance profile may cause a solution of star-shaped gold nanoparticles to appear blue. The absorbance profile of gold nanoparticles is morphology dependent. Morphology may include size and shape. Thus, nanoparticles may be modified to optimize fluorescence quenching or to tailor the light filtering spectrum of the final product. Such modifications may include changes in morphology. Selection of nanoparticles for use in the methods and materials described herein allows control over the light filtering characteristics of the nanoparticles.

[0019] The present disclosure relates to chemical dyes. The chemical dyes may include rhodamine-based dyes with a peak absorbance at 554 nm. As a non-limiting example, the dyes may include rhodamine B. Rhodamine B is non-toxic, highly water-soluble and heat- and light-stable, allowing for long-term specific light filtering in biomaterials. The dyes may be fluorescent. The fluorescence of the dye may include an emission peak that may substantially overlap with the absorbance peak of the gold nanoparticles, resulting in fluorescence quenching. Providing a combination of gold nanoparticles and dyes as described herein may result in a material with a weakened color when compared to rhodamine B alone, any such other dyes with bright fluorescent colors, or any such other commercially available light filtering materials for contact lenses. In some embodiments, the final color may include purple. The identity of the dye may be reasonably modified or combined with any other dyes (e.g., rhodamine 6G) to adjust the light filtering characteristics.

[0020] The present disclosure further relates to stabilization mechanisms. The stabilization mechanism may include a nanoparticle coating. The nanoparticle coating material may include a polymer. Such a polymer may include a terminal thiolated poly(ethylene glycol) (PEG) polymer, although other such polymers known in the art may be used. The PEG polymer may stabilize the gold nanoparticles through steric hindrance. PEG is a highly stable biocompatible polymer that can be well dispersed in both aqueous media and contact lens precursor materials. As a non-limiting example, the contact lens precursor may include HEMA-based Etafilcon A.

[0021] Thus, the disclosed method and material relates to the use of a combination of chemical dyes and gold nanoparticles to produce a specific light filtering material. Fluorescence quenching can be the result of the proximity of the chemical dye to the nanoparticle surface. The disclosed method relates to the conjugation of dyes to the surface of the provided gold nanoparticles. Such conjugation can result in a reduction in the fluorescence (and therefore color intensity) of the light filtering material. Such conjugated light filtering material can maintain light filtering ability. The use of a specific gold nanoparticle shape further enables such fluorescence quenching.

[0022] The disclosed methods and materials can be customized for cosmetic and / or therapeutic contact lenses. Chemical integration into biomaterials can allow for immobilization and selective patterning of light filtering materials. The disclosed methods and materials relate to the integration of light filtering materials into various biomaterials. The disclosed methods and materials further relate to the combination of various dyes and / or various gold nanoparticles. Such combinations can allow for tunable and highly complex light filtering spectra. The various gold nanoparticles can include various gold nanoparticles of various shapes. The disclosed methods and materials relate to long-term stability and material integration. The long-term stability and material integration allows for passive sensing applications and / or labeling of commercial products, among other uses.

[0023] The present disclosure relates to anchoring mechanisms. Such mechanisms may allow nanoparticles to be chemically integrated into biomaterials (as opposed to physical integration via chain entanglement). Such mechanisms may include polymers. As a non-limiting example, methacryloyl-derived monomers (glycidyl methacrylate) may be selected as an anchoring mechanism for incorporating the materials described herein into biomaterials. Such biomaterials may include HEMA-based contact lenses. Methacrylate chemical groups contain C=C double bonds that may participate in UV-induced polymerization of contact lenses. Furthermore, since methacrylate is a typical component of HEMA-based contact lenses. Integration of these light filtering materials using methacrylates does not significantly affect the final product. The method may include maintaining the clarity and transparency of the final material by using such anchoring mechanisms. As a further non-limiting example, poly(vinyl alcohol) (PVA) may be utilized to achieve chemical integration. PVA may further stabilize the nanoparticles. PVA may also provide an anchoring mechanism that can be attached to free hydroxyl (-OH) groups for chemical integration into biomaterials. Other polymers known in the art may also be used.

[0024] The method may further include providing a nanoparticle coating material. For example, the nanoparticle coating material may be poly(vinyl alcohol) (PVA). PVA is known to be stable and highly compatible with HEMA-based contact lens materials. PVA can stabilize gold nanoparticles, conjugate chemical dyes via carbonyldiimidazole-mediated esterification, and conjugate monomers via transesterification.

[0025] 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 be anisotropic. Such shapes may include star shapes. Alternative shapes are known in the art and may include, but are not limited to, cube shapes, nanorod shapes, octahedron shapes, decahedron shapes, cuboctahedron shapes, tetrahedron shapes, rhombic dodecahedron shapes, truncated bisquare prism shapes, or truncated double tetrahedron 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 650 nm up to about 800 nm. Alternative ranges exist and may include, but are not limited to, about 675 nm up to about 800 nm, about 700 nm up to about 800 nm, about 725 nm up to about 800 nm, about 750 nm up to about 800 nm, about 775 nm up to about 800 nm, about 650 nm up to about 775 nm, about 650 nm up to about 750 nm, about 650 nm up to about 725 nm, about 650 nm up to about 700 nm, or about 650 nm up to about 675 nm. The present disclosure further relates to chemical dyes. The chemical dyes may block light in the range of about 530 nm up to about 560 nm. Alternative ranges exist and may include, but are not limited to, about 540 nm up to about 560 nm, about 550 nm up to about 560 nm, about 530 nm up to about 550 nm, about 530 nm up to about 550 nm, or about 530 nm up to about 540 nm. The chemical dye may further emit light. Light emission may occur via fluorescence, phosphorescence, and other known phenomena. The emission of the chemical dye may occur such that it sufficiently overlaps with the light filtering range of the gold nanoparticles. Such chemical dyes may include organic chemical dyes. As non-limiting examples, organic chemical dyes may include rhodamine-based dyes, including, but not limited to, rhodamine 6G, rhodamine B, tetramethylrhodamine (TRITC), and 5-carboxy-tetramethylrhodamine.The chemical dyes may also include any dye that can be functionalized with N-hydroxysuccinimide (NHS). 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 terminally thiolated poly(ethyleneglycol) (PEG-SH). Alternative polymers are known in the art and may include, but are not limited to, poly(ethylene glycol) (PEG), polycarbonate, poly(vinyl alcohol) (PVA), 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 PVP having a molecular weight of about 55 kDa up to about 1300 kDa. The present disclosure relates to methods of attaching gold nanoparticles to stabilization mechanisms. Attachment may occur via chemical conjugation. Such attachment may be selective. Such attachment may improve the colloidal and / or thermal stability of the nanoparticles, as well as biocompatibility. The present disclosure relates to anchoring mechanisms. Such anchoring mechanisms may include methacrylates. Such anchoring mechanisms may include methacryloyl-derivatized monomers. As non-limiting examples, anchoring mechanisms may include polyvinyl alcohol (PVA) or glycidyl methacrylate. Such methacrylates may further include thiolated methacrylate dimers. Such thiolated methacrylate dimers 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 The anchoring mechanism may include, but is not limited to, 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 attaching a gold nanoparticle to an anchoring mechanism. The present disclosure further relates to the attachment of an anchoring mechanism to an organic dye. In such attachment, the anchoring mechanism attached to the organic dye may further be attached to the gold nanoparticle. The attachment may occur via chemical conjugation. Such attachment may be selective. Such attachment may improve the colloidal and / or thermal stability of the nanoparticles, as well as biocompatibility. The present disclosure further relates to a method of attaching an anchoring mechanism to a base material. The base material may include a biomaterial as described above. The conjugation of the gold nanoparticles and the anchoring mechanism to the base material may include cross-linking. Such cross-linking may facilitate the integration of the nanoparticles into the base material.

[0026] The present disclosure relates to compositions, which may include a base material, nanoparticles, chemical dyes, nanoparticle coating materials (i.e., stabilization mechanisms), anchoring mechanisms, or any combination thereof. Such compositions may include chemical dyes that emit light with an emission spectrum that sufficiently overlaps with the gold nanoparticles to which it is conjugated. This may result in quenching. 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 length of the major and minor axes, volume, sharpness, and / or other relevant features. 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 , about 4,250nm 3 ~Maximum approx. 30,000nm 3 , about 5,250nm 3 ~Maximum approx. 30,000nm 3 , about 6,250nm 3 ~Maximum approx. 30,000nm 3 , about 7,250nm 3 ~Maximum approx. 30,000nm 3 , about 8,250nm 3 ~Maximum approx. 30,000nm3 , about 9,250nm 3 ~Maximum about 30,000nm 3 , about 10,250nm 3 ~Maximum about 30,000nm 3 , about 11,250nm 3 ~Maximum about 30,000nm 3 , about 12,250nm 3 ~Maximum about 30,000nm 3 , about 13,250nm 3 ~Maximum about 30,000nm 3 , about 14,250nm 3 ~Maximum about 30,000nm 3 , about 15,250nm 3 ~Maximum about 30,000nm 3 , about 16,250nm 3 ~Maximum about 30,000nm 3 , about 17,250nm 3 ~Maximum about 30,000nm 3 , about 18,250nm 3 ~Maximum about 30,000nm 3 , about 19,250nm 3 ~Maximum about 30,000nm 3 , about 20,250nm 3 ~Maximum about 30,000nm 3 , about 21,250nm 3 ~Maximum about 30,000nm 3 , about 22,250nm 3 ~Maximum about 30,000nm 3 , about 23,250nm 3 ~Maximum about 30,000nm 3 , about 24,250nm 3 ~Maximum about 30,000nm 3 , about 25,250nm 3 ~Maximum about 30,000nm 3 , about 26,250nm 3 ~Maximum about 30,000nm 3 , about 27,250nm 3 ~Maximum about 30,000nm 3 , about 28,250nm 3 ~Maximum about 30,000nm 3 , 又は About 29,250nm3 ~Maximum approx. 30,000nm 3 can be adjusted to.

[0027] The final light blocking profile can be tailored through the use of various nanoparticles, chemical dyes, nanoparticle coating materials (i.e., stabilization mechanisms), anchoring mechanisms, and combinations thereof. Such tailoring can result in Full-Width at Half Maximum (FWHM) values ​​of about 58 nm up to about 118 nm. As non-limiting examples, FWHM values ​​can range from about 58 nm up to about 108 nm, about 58 nm up to about 98 nm, about 58 nm up to about 88 nm, about 58 nm up to about 78 nm, or about 58 nm up to about 68 nm.

[0028] 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).

[0029] 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.

[0030] The following definitions are provided for terms used in this disclosure.

[0031] 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.

[0032] As used herein, the term "(meth)" refers to optional methyl substitution. Thus, terms such as "(meth)acrylate" refer to both methacrylate and acrylate.

[0033] The term "individual" includes humans and vertebrate animals.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] As used herein, "antimicrobial" means intended to kill or reduce the harmful effects of bacteria.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] As used herein, the term "wetting agent" refers to a material that reduces the surface tension of water, thus allowing the 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 water, thus aiding the spreading of water-based solutions.

[0044] "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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] A "polymer" is an organic compound having a number average molecular weight greater than 1500 and may be reactive or non-reactive.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] A "polymer" is a target macromolecule composed of repeating units of the monomers used during polymerization. Exemplary polymers may include poly(ethylene glycol) (PEG), polycarbonate, poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), polystyrene (PS), polycaprolactone (PCL), ethylene oligomers or polyethylene (PE), polypropylene (PP), poly(methyl methacrylate) (PMMA), and other polymers known in the art.

[0054] 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.

[0055] 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.

[0056] A "repeating unit" is the smallest grouping of atoms within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0057] 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.

[0058] 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.

[0059] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can be further reacted to form a polymer.

[0060] 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.

[0061] "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).

[0062] "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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0069] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0070] 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 1-16 carbon atoms. Preferably, the alkyl group contains 1-10 carbon atoms, alternatively 1-7 carbon atoms, or alternatively 1-4 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 1, 2, or 3 groups independently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halogen, phenyl, benzyl, thiol, and combinations thereof. "Alkylene" means a divalent alkyl group, e.g., -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, and -CH2CH2CH2CH2-.

[0071] "Haloalkyl" refers to an alkyl group, as defined above, substituted with one or more halogen atoms, each halogen being 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" includes perhaloalkyl groups, such as -CF3- or -CF2CF3-. "Haloalkylene" refers to a divalent haloalkyl group, such as -CH2CF2-.

[0072] "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 3 to 12 ring carbon atoms. Preferred are C3-C8 cycloalkyl groups, C3-C7 cycloalkyl, more preferably C4-C7 cycloalkyl, and even more preferably C5-C6 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.

[0073] "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.

[0074] "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.

[0075] "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.

[0076] "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.

[0077] "Alkylamine" refers to an alkyl group attached to the parent molecular moiety through an -NH bridge. Alkyleneamine refers to a divalent alkylamine group, such as -CHCHNH-.

[0078] "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.

[0079] 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.

[0080] "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 R A Group(R A is replaced by (as defined in options (b) to (i) of Formula A).

[0081] "Silyl" refers to a structure of formula RSi- and "siloxy" refers to a structure of formula RSi-O-, where each R in silyl or siloxy is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably ethyl or methyl), and C3-C8 cycloalkyl.

[0082] "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-[CH2CHO] p - or CH3O-[CH2CH2O] p Examples of alkyleneoxy include polymethyleneoxy, polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0083] "Oxaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced with an oxygen atom, such as -CHCHOCH(CH)CH-. "Thiaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced with a sulfur atom, such as -CHCHSCH(CH)CH-.

[0084] 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 include one or more alkylenes, haloalkylenes, amides, amines, alkyleneamines, carbamates, carboxylates (-CO2-), disulfides, arylenes, heteroarylenes, cycloalkylenes, heterocycloalkylenes, alkyleneoxys, oxaalkylenes, thiaalkylenes, haloalkyleneoxys (alkyleneoxys substituted with one or more halo groups, e.g., -OCF2-, -OCF2CF2-, -OCF2CH2-), siloxanyls, alkylenesiloxanyls, thiols, or combinations thereof. The linking group may be optionally substituted with one or more substituents. Suitable substituents can include those independently selected from alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, CHO-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy- (wherein there can 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 can also be substituted with a polymerizable group (in addition to the polymerizable group to which it is attached), such as (meth)acrylate.

[0085] Preferred linking groups include C1-C8 alkylene (preferably C2-C6 alkylene) and C1-C8 oxaalkylene (preferably C2-C6 oxaalkylene), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Preferred linking groups also include carboxylate, amide, C1-C8 alkylene-carboxylate-C1-C8 alkylene, or C1-C8 alkyleneamide-C1-C8 alkylene.

[0086] 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 2 and -L are preferably Rg-alkylene-cycloalkylene-, where -L 2 -Rg is preferably -cycloalkylene-alkylene-Rg.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] As used herein, "fluorescence" refers to a type of luminescence that occurs in gas, liquid, or solid matter. Fluorescence occurs after the absorption of a light wave (i.e., a photon) that can promote an electron from a ground state to an excited state. In fluorescence, the electron's spin is still paired with the ground state electron, unlike phosphorescence. When the excited electron returns to the ground state, it emits a lower energy photon that corresponds to a longer wavelength than the absorbed photon.

[0094] As used herein, "phosphorescence" refers to the phenomenon of delayed emission corresponding to the radiative decay of excited electrons from a molecular triplet state. As a general property, phosphorescence represents a challenge in chemical physics due to the spin-forbidden nature of the underlying triplet-singlet photon emission and because its analysis involves deep knowledge of electronic molecular structure. Phosphorescence is the simplest physical process that provides an example of spin-forbidden transformation with characteristic spin selectivity and magnetic field dependence, and is also a model for more complex chemical reactions and spin catalysis applications. Phosphorescence is generally seen as an alternative method of photon emission with respect to fluorescence. Methods exist in the art to increase the amount of fluorescent versus phosphorescent emission, such as the use of heavy metals to increase spin coupling.

[0095] 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.

[0096] "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)).

[0097] 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.

[0098] 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.

[0099] As used herein, the term "organic dye" refers to organic compounds that have color because they absorb light in the visible spectrum, have at least one chromophore (color-carrying group), have a conjugated system, and exhibit electronic resonance, which is a stabilizing force in organic compounds (Abrahart, 1977). Organic dyes used in gel-like matrices may exhibit leaching, in which case the dye slowly leaves the gel-like matrix. Exemplary organic dyes may include rhodamine-based dyes, such as rhodamine B and rhodamine G6.

[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 resonances that allow 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 can include, but are not limited to, AgNO3, 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 blocking at one or more wavelengths or ranges of wavelengths in the electromagnetic spectrum. The percentage 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] As used herein, "ligand" refers to an ion or neutral molecule that binds to a central metal atom or ion. Exemplary ligands may include PVP, PVA, DSDMA, and other molecules that can bind to the central metal atom. The metal atom may include a variety of metals, including, but not limited to, noble metals such as gold. The ligand has at least one donor that has an electron pair that is used to form a covalent bond with the central metal atom.

[0110] As used herein, "intermediate ligand" refers to a ligand temporarily conjugated to a metal atom that is further exchanged to allow for the conjugation of an alternative ligand.

[0111] 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).

[0112] 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.

[0113] 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%.

[0114] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0115] 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).

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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. Silicone-containing components may contain, for example, 1 to 220 siloxane repeat units, such as those defined below. Silicone-containing components may also contain at least one fluorine atom.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] Formula A. The silicone-containing component may include one or more polymerizable compounds of formula A:

[0124] [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) C1-C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 16 Alkyl, (c) C-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 12 Cycloalkyl, (d) C6-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. 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.

[0125] 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.

[0126] Formula B. The silicone-containing component of formula A may be a monofunctional polymerizable compound of formula B:

[0127] [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 is independently, in each occurrence, C1-C6 alkyl, C3-C 12 Cycloalkyl, C1-C6 alkoxy, C4-C 12cyclic 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 group 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, C1-C8 alkyl (eg, C1-C4 alkyl, or butyl, or methyl), or aryl (eg, phenyl), where the alkyl and aryl may be optionally substituted with one or more fluorine atoms.

[0128] 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.

[0129] 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.

[0130] B-3. ​​Compounds of formula B, B-1, and B-2 may include compounds of formula B-3, wherein R A1 , R A2 , RA3 , and R A4 is independently, at each occurrence, C1-C6 alkyl or siloxy. Preferred alkyl is C1-C3 alkyl, or more preferably methyl. Preferred siloxy is trimethylsiloxy.

[0131] 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 CH3O-[CH2CH2O] p Compounds of formula B, B-1, B-2, or B-3, which are methoxy-capped polyethyleneoxyalkyl of -CH2CH2CH2, where p is an integer from 1 to 50.

[0132] 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.

[0133] 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 is independently C1-C6 alkyl, alternatively C1-C4 alkyl, or alternatively butyl or methyl.

[0134] 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 A6is a C1-C8 alkyl, preferably a C1-C6 alkyl, more preferably a C1-C4 alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl). A6 is n-butyl.

[0135] 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.

[0136] When Rg is (meth)acrylamide, the nitrogen group is R A9 and R A9 is H, C1-C8 alkyl (preferably C1-C4 alkyl, e.g., n-butyl, n-propyl, methyl, or ethyl), or C3-C8 cycloalkyl (preferably C5-C6 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).

[0137] 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 selected from the group consisting of alkylene (preferably C1-C4 alkylene), cycloalkylene (preferably C5-C6 cycloalkylene), alkyleneoxy (preferably ethyleneoxy), haloalkyleneoxy (preferably haloethyleneoxy), amide, oxaalkylene (preferably containing 3-6 carbon atoms), ), siloxanyl, alkylenesiloxanyl, carbamate, alkyleneamine (preferably C1-C6 alkyleneamine), or a combination of two or more thereof, wherein the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, siloxy, and carbamate.

[0138] 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).

[0139] 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, 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 C1-C6 alkylene, preferably C1-C3 alkylene, more preferably n-propylene.

[0140] B-12. The 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 CH2CH2N(H)-C(=O)-O-CH2CH2-O-CH2CH2CH2.

[0141] B-13. The 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 CH2CH2-O-CH2CH2CH2.

[0142] 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. An example of such a linking group is -(CH2)3-[Si(CH3)2-O-Si(CH3)2-(CH2)2] q -It is.

[0143] 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, 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 the linking group is alkyleneoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene, where the cycloalkylene is optionally substituted with one, two, or three independently selected alkyl groups, preferably C1-C3 alkyl, more preferably methyl. An example of such a linking group is -[OCH2CH2] q -OC(=O)-NH-CH2-[1,3-cyclohexylene]-NHC(=O)O-CH2CH2-O-CH2CH2-, where the cyclohexylene is substituted with three methyl groups at the 1 and 5 positions.

[0144] 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, the linking group is alkyleneoxy, and each alkylene in the alkyleneoxy is independently optionally substituted with hydroxyl. An example of such a linking group is -O-(CH2)3-. Another example of such a linking group is -O-CH2CH(OH)CH2-O-(CH2)3-.

[0145] B-17. The 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, in which Rg comprises styryl and the linking group is an alkyleneamine. An example of such a linking group is -NH-(CH2)3-.

[0146] 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). An example of such a linking group is -CH2CH(G)CH2-O-(CH2)3-, in which G is hydroxyl. In another example, G is R3SiO-, two R groups are trimethylsiloxy and the third is C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl) or the third is C3-C8 cycloalkyl. In a further example, G is R3Si-(CH2)3-O-CH2CH(OH)CH2-O-, two R groups are trimethylsiloxy and the third is C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl) or C3-C8 cycloalkyl. In yet a further example, G is a polymerizable group such as a (meth)acrylate. Such compounds can function as crosslinkers.

[0147] 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-CH2CH(OH)CH2-O-(CH2)3-.

[0148] 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. An example of such a linking group is -O-(CH2)2-N(H)C(=O)O-(CH2)2-O-(CH2)3-.

[0149] B-21. The 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. An example of such a linking group is -(CH2)2-N(H)C(=O)O-(CH2)2-O-(CH2)3-.

[0150] 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:

[0151] [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 , RA6 , R A7 , and R A9 is as defined in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0152] C-1. Compounds of formula C may include (meth)acrylates of formula C-1, which are compounds of formula C where Z is O.

[0153] 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.

[0154] C-3. Compounds of formula C may include (meth)acrylamides of formula C-3, where Z is N(R A9 ) and R A9 is a C1-C8 alkyl group that is unsubstituted or optionally substituted as described above. A9 Examples of R include CH3, -CH2CH(OH)CH2(OH), -(CH2)3-siloxanyl, -(CH2)3-SiR3, and -CH2CH(OH)CH2-O-(CH2)3-SiR3, where each R in the foregoing groups is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl), and C3-C8 cycloalkyl. A9 Further examples include -(CH2)3-Si(Me)(SiMe3)2 and -(CH2)3-Si(Me2)-[O-SiMe2] 1-10 -CH3 is an example.

[0155] Formula D. Compounds of formula C may include compounds of formula D:

[0156] [ka] During the ceremony, R A8 is hydrogen or methyl, Z1 is O or N(R A9 ) and L 1 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.).

[0157] D-1. Compounds of formula D may include compounds of formula D-1, wherein L 1 is a C2-C5 alkylene optionally substituted with hydroxyl. 1 is n-propylene optionally substituted with hydroxyl.

[0158] 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 -(CH2)2-O-(CH2)3-, and -CH2CH(OH)CH2-O-(CH2)3-.

[0159] D-3. Compounds of formula D, D-1, and D-2 may include compounds of formula D-3, wherein Z 1 is O.

[0160] D-4. Compounds of formula D, D-1, and D-2 may include compounds of formula D-4, wherein Z 1 N(RA9 ) and R A9 is H.

[0161] 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 is a C1-C4 alkyl optionally substituted with one or two substituents selected from hydroxyl, siloxy, and C1-C6 alkyl-siloxanyl-.

[0162] 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.

[0163] 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.

[0164] 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 is independently C1-C6 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.

[0165] 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 is independently C1-C6 alkyl (e.g., methyl or ethyl) or siloxy (e.g., trimethylsiloxy), and R A5 , R A6 , and R A7 is independently C1 to C6 alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).

[0166] 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:

[0167] [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.

[0168] E-1. Compounds of formula E may include compounds of formula E-1, wherein Rg and Rg 1are compounds of formula E, which are vinyl carbonates of the structure CH2=CH-OC(=O)-O- or CH2=C(CH3)-OC(=O)-O-, respectively.

[0169] E-2. Compounds of formula E may include compounds of formula E-2, wherein Rg and Rg 1 are each (meth)acrylates.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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 are independently at each occurrence C1-C6 alkyl, preferably they are independently C1-C3 alkyl, or preferably each is methyl.

[0174] 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 CH3O-[CH2CH2O] p A compound of formula E, E-1, E-2, E-3, E-4, E-5, or E-6 which is a methoxy-capped polyethyleneoxyalkyl of the formula -CH2CH2CH2, where p is an integer from 1 to 50, or 1 to 30, or 1 to 10, or 6 to 10.

[0175] 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.

[0176] 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 L 2 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.

[0177] 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 SiO 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.

[0178] [Table 1-1]

[0179] [Table 1-2]

[0180] 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.

[0181] [Table 2-1]

[0182] [Table 2-2]

[0183] The silicone-containing component can have an average molecular weight of about 400 to about 4000 Daltons.

[0184] 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.

[0185] 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.

[0186] Examples of suitable acyclic polyamides include polymers and copolymers comprising repeat units of formulae G1 and G2,

[0187] [ka] In the formula, X is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is a C1-C3 alkyl group, and R 40 is selected from H, linear or branched, substituted or unsubstituted C1-C4 alkyl groups, R 41 is selected from H, linear or branched, substituted or unsubstituted C1-C4 alkyl groups, amino groups having up to 2 carbon atoms, amido groups having up to 4 carbon atoms, and alkoxy groups having up to 2 carbon atoms; R 42 is selected from H, linear or branched, substituted or unsubstituted C1-C4 alkyl groups, or selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 43 is selected from H, linear or branched, substituted or unsubstituted C1-C4 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 43The 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.

[0188] R 40 and R 41 may be independently selected from H, a substituted or unsubstituted C1-C2 alkyl group. X may be a direct bond, R 40 and R 41 may be independently selected from H, a substituted or unsubstituted C1-C2 alkyl group. 42 and R 43 may be independently selected from H, a substituted or unsubstituted C1-C2 alkyl group, methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0189] The acyclic polyamides of the invention may comprise a majority of repeat units of formula LV or formula LVI, or the acyclic polyamides may comprise at least 50 mole percent of repeat units of formula G or formula G1, such as at least about 70 mole percent and at least 80 mole percent. Specific examples of repeat units of formula G and formula G1 include repeat units derived from 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 acrylamide of formulas G2 and G3.

[0190] [ka]

[0191] Examples of suitable cyclic amides that can be used to form the cyclic polyamides include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. Examples of suitable cyclic polyamides include polymers and copolymers comprising repeat units of formula G4:

[0192] [ka] In the formula, R 45 is a hydrogen atom or a methyl group, f is a number from 1 to 10, and X is a direct bond, -(CO)-, or -(CONHR 46 )- and R 46 is a C1-C3 alkyl group. In formula LIX, f can be 8 or less, including 7, 6, 5, 4, 3, 2, or 1. In formula G4, f can be 6 or less, including 5, 4, 3, 2, or 1. In formula G4, f can be 2-8, including 2, 3, 4, 5, 6, 7, or 8. In formula LIX, f can be 2 or 3. When X is a direct bond, f can be 2. In such cases, the cyclic polyamide can be polyvinylpyrrolidone (PVP).

[0193] 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.

[0194] 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).

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] Crosslinking Agent Generally, it is desirable to add one or more crosslinking agents, also referred to as crosslinking monomers, multifunctional macromers, and prepolymers, to the reactive mixture. The crosslinking agents may be selected from difunctional crosslinkers, trifunctional crosslinkers, tetrafunctional crosslinkers, and mixtures thereof, including silicone-containing and non-silicone-containing crosslinkers. Non-silicone-containing crosslinkers include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glycerol trimethacrylate, methacryloxyethyl vinyl carbonate (HEMAVc), allyl methacrylate, methylene bisacrylamide (MBA), and polyethylene glycol dimethacrylate, where the polyethylene glycol has a molecular weight of up to about 5000 Daltons. The crosslinking agents are used in the reactive mixture in conventional amounts, for example, from about 0.000415 to about 0.0156 moles per 100 grams of reactive formulation. Alternatively, if hydrophilic monomer and / or silicone-containing component is multifunctional due to molecular design or impurities, adding crosslinker to reactive mixture is optional.Examples of hydrophilic monomer and macromer that can act as crosslinker and do not require adding additional crosslinker to reactive mixture when present include (meth)acrylate and (meth)acrylamide end-capped polyether.Other crosslinkers will be known to those skilled in the art and can be used to make the silicone hydrogel of the present invention.

[0200] It may be desirable to select a crosslinker that has a similar reactivity with one or more of the other reactive components in the formulation. In some cases, it may be desirable to select a mixture of crosslinkers with different reactivities to control some physical, mechanical, or biological properties of the resulting silicone hydrogel. The structure and morphology of the silicone hydrogel may also be affected by the diluent and curing conditions used.

[0201] To further increase the modulus and maintain tensile strength, multifunctional silicone-containing components, including macromers, crosslinkers, and prepolymers, may also be included. Silicone-containing crosslinkers may be used alone or in combination with other crosslinkers. An example of a silicone-containing component that can act as a crosslinker and does not require the addition of a crosslinking monomer to the reactive mixture when present, includes α,ω-bismethacryloxypropyl polydimethylsiloxane.

[0202] Crosslinkers with rigid chemical structures and polymerizable groups that undergo free radical polymerization may also be used. Non-limiting examples of suitable rigid structures include crosslinkers containing phenyl and benzyl moieties, such as 1,4-phenylenediacrylate, 1,4-phenylenedimethacrylate, 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, and combinations thereof. Rigid crosslinkers may be included in an amount of about 0.5 to about 15, or about 2 to 10, 3 to 7, based on the total weight of all reactive components. The physical and mechanical properties of the silicone hydrogels of the present invention may be optimized for a particular application by adjusting the components in the reactive mixture.

[0203] Non-limiting examples of silicone crosslinkers also include the multifunctional silicone-containing components described above, such as the compounds of formula E (and subformulas thereof) and the multifunctional compounds shown in the table above.

[0204] 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. 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

[0205] 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

[0206] 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.

[0207] 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 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having an emission peak that at least partially overlaps with the peak optical absorption of the plurality of gold nanoparticles; and a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

[0208] Aspect 2: The composition of aspect 1, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm.

[0209] Embodiment 3: The composition according to any one of embodiments 1 to 2, wherein the base material comprises a biological material.

[0210] Embodiment 4: The composition according to any one of embodiments 1 to 2, wherein the base material comprises a biomaterial matrix.

[0211] Embodiment 5: The composition of any one of embodiments 1 to 2, wherein the base material comprises a hydrogel.

[0212] Embodiment 6: The composition of any one of embodiments 1 to 2, wherein the base material comprises a silicone-based hydrogel.

[0213] Embodiment 7: The composition of any one of embodiments 1 to 2, wherein the base material comprises a HEMA-based material.

[0214] Example 8: The composition of any one of Examples 1-7, wherein at least a portion of the plurality of gold nanoparticles have a star shape.

[0215] Aspect 9: The composition of claim 1, wherein the shape of at least a portion of the plurality of gold nanoparticles is adjusted such that a portion of the plurality of gold nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm.

[0216] Embodiment 10: The composition of claim 1, wherein the chemical dye comprises a rhodamine-based dye.

[0217] Embodiment 11: The composition of claim 1, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC.

[0218] Embodiment 12: The composition of claim 1, wherein the nanoparticle coating material comprises a terminally thiolated poly(ethylene glycol).

[0219] Embodiment 13: The composition of claim 1, wherein the nanoparticle coating material comprises poly(vinylpyrrolidone).

[0220] Embodiment 14: The composition of claim 1, wherein the shape of at least a portion of the plurality of gold nanoparticles is tailored to provide fluorescence quenching.

[0221] Embodiment 15: A method of making the composition of claim 1.

[0222] Aspect 16: A composition for light filtering, the composition comprising: a base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak light absorption value in a range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having an abortion peak in a range of about 530 nm to about 560 nm; and a nanoparticle coating material disposed on at least a portion of the plurality of nanoparticles.

[0223] Aspect 17: The composition of claim 16, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm.

[0224] Embodiment 18: The composition of claim 16, wherein the base material comprises a biomaterial.

[0225] Embodiment 19: The composition of claim 16, wherein the base material comprises a biomaterial matrix.

[0226] Embodiment 20: The composition of claim 16, wherein the base material comprises a hydrogel.

[0227] Aspect 21: The composition of claim 16, wherein the base material comprises a HEMA-based material.

[0228] Embodiment 22: The composition of claim 16, wherein at least a portion of the plurality of nanoparticles have a star shape.

[0229] Embodiment 23: The composition of claim 16, wherein the shape of at least a portion of the plurality of nanoparticles is adjusted such that a portion of the plurality of nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm.

[0230] Embodiment 24: The composition of claim 16, wherein the chemical dye comprises a rhodamine-based dye.

[0231] Embodiment 25: The composition of claim 16, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC.

[0232] Embodiment 26: The composition of claim 16, wherein the nanoparticle coating material comprises a terminally thiolated poly(ethylene glycol).

[0233] Aspect 27: The composition of claim 16, wherein the nanoparticle coating material comprises poly(vinylpyrrolidone).

[0234] Embodiment 28: The composition of claim 16, wherein the shape of at least a portion of the plurality of nanoparticles is tailored to provide fluorescence quenching.

[0235] Embodiment 29: The composition of claim 16, wherein the nanoparticles comprise plasmonic nanoparticles.

[0236] Embodiment 30: The composition of claim 16, wherein the nanoparticles comprise metal nanoparticles.

[0237] Embodiment 31: The composition of claim 16, wherein the nanoparticles comprise gold nanoparticles.

[0238] Embodiment 32: A method of making the composition of claim 16.

[0239] Aspect 33: A composition for light filtering, the composition comprising: a base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak light absorption value in a range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having a spectral peak that is at least partially quenched by filtering of a spectral curve of the nanoparticles; 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 nanoparticles.

[0240] Embodiment 34: The composition of claim 33, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm.

[0241] Embodiment 35: The composition of claim 33, wherein the base material comprises a biomaterial.

[0242] Embodiment 36: The composition of claim 33, wherein the base material comprises a biomaterial matrix.

[0243] Embodiment 37: The composition of claim 33, wherein the base material comprises a hydrogel.

[0244] Aspect 38: The composition of claim 33, wherein the base material comprises a HEMA-based material.

[0245] Embodiment 39: The composition of claim 33, wherein at least a portion of the plurality of nanoparticles have a star shape.

[0246] Embodiment 40: The composition of claim 33, wherein the shape of at least a portion of the plurality of nanoparticles is adjusted such that a portion of the plurality exhibits a peak optical absorption in the range of about 650 nm to about 800 nm.

[0247] Embodiment 41: The composition of claim 33, wherein the chemical dye comprises a rhodamine-based dye.

[0248] Embodiment 42: The composition of claim 33, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC.

[0249] Embodiment 43: The composition of claim 33, wherein the fixing mechanism comprises glycidyl methacrylate.

[0250] Embodiment 44: The composition of claim 33, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

[0251] Embodiment 45: The composition of claim 33, wherein the shape of at least a portion of the plurality of nanoparticles is tailored to provide fluorescence quenching.

[0252] Embodiment 46: The composition of claim 33, wherein the nanoparticles comprise plasmonic nanoparticles.

[0253] Embodiment 47: The composition of claim 33, wherein the nanoparticles comprise metal nanoparticles.

[0254] Embodiment 48: The composition of claim 33, wherein the nanoparticles comprise gold nanoparticles.

[0255] Embodiment 49: A method of making the composition described in claim 33.

[0256] Specific photoblocking of dyes accompanied by fluorescence quenching of gold nanoparticles was the strategy designed to generate patient-compatible lenses (Figure 1A-C).

[0257] 1A-1C show a surface modification strategy according to an embodiment of the present disclosure, which was designed to artificially block the area between the red and green cones to improve contrast as it relates to red-green color vision deficiency.

[0258] 2A-2B show the selection of gold nanostars as a platform for a light-blocking material according to an embodiment of the present disclosure. Gold nanostars were selected as a platform for the light-blocking material, as can be seen in FIG. 2A, which shows the ultraviolet-visible (UV-Vis) absorbance spectrum of a solution of gold nanostars normalized to the localized surface plasmon resonance (LSPR) peak. The peak was close enough to the target region (and the emission spectrum of the dye) for Förster Resonance Energy Transfer (FRET) (i.e., fluorescence quenching) to occur, but removed enough so as not to contribute significantly to the overall light-blocking profile. The nanostars blocked the red light region, so the solution appeared blue. A representative Transmission Electron Microscopy (TEM) micrograph of gold (Au) nanostars can be seen in FIG. 2B.

[0259] Gold nanostars were chosen as the light blocking material. Gold nanostars blocked light with wavelengths longer than the target region (530-560 nm), as can be seen in Figure 2A. However, the LSPR peak was close enough to the emission spectrum of the fluorescent dye that fluorescence quenching could still occur via FRET. TEM micrographs of the gold nanostars confirmed the expected morphology (small core with 4-6 branches, approximately 10-20 nm each), as can be seen in Figure 2B. The size and length of the branches may be modified to block different red light regions to adapt the color profile and achieve FRET fluorescence quenching with different dyes. As a non-limiting example, these modifications in the size and length of the gold nanostar branches may be the result of a change in the amount of seeds used. To demonstrate this, gold nanostars were grown keeping all parameters the same but changing the amount of seeds added from 36 μl to 360 μl (Figure 3), resulting in a variety of sizes and "spikyness" of the resulting gold nanostars. TEM images were made to display the morphology of gold nanostars synthesized at 36 μl (FIG. 4A), 100 μl (FIG. 4B), 150 μl (FIG. 4C), and 360 μl (FIG. 4D).

[0260] Nanostars were first synthesized using thiol-terminated poly(ethylene glycol) (PEG-SH).Cystamine or another suitable small multifunctional compound was then used to tether organic dyes to the nanostar surface, as described below.

[0261] Stock solutions of 15 mM cystamine and 0.15 mM rhodamine BN-hydroxysuccinimide (RhoB-NHS) were prepared in 100 mM NaHCO3 buffer in MilliQ. Cystamine (2 ml) and RhoB-NHS (1 ml) were then mixed in a scintillation vial and reacted at 4°C for 4 hours.

[0262] In a 20 ml scintillation vial, 2 mM trisodium citrate (1 ml), 25.4 mM HAuCl4 (0.188 ml), and 0.1 M ice-cold NaBH4 (60 μl) were added sequentially to MilliQ (18.822 ml). The solution was vigorously stirred until the reaction was complete to form nanoseeds. In a second 20 ml scintillation vial, 11 mM HAuCl4 (0.64 ml), 10 mM AgNO3 (0.2 ml), and 0.1 M L-ascorbic acid (0.103 ml, added dropwise) were added sequentially to 7.33 mM CTAB (15 ml). Upon addition of the last drop of L-ascorbic acid, the solution became clear and the desired volume of nanoseeds was added (e.g., 150 μl). These samples were gently stirred until the reaction was complete. The nanoparticles were then centrifuged (15,000 rpm for 10 min), the supernatant removed, and the nanoparticles resuspended in a mixture of dye-cystamine (3 ml) and either 100 mM PEG-SH or polyvinylpyrrolidone (PVP) (1 ml in MilliQ). Samples were left in a fume hood overnight and used the next day.

[0263] Dye-conjugated NPs were centrifuged at 12,000 × g for 15 min and resuspended in 5 ml of MilliQ until loss of color in the supernatant (approximately 3–4 times). Aliquots (300 μl) of purified dye-NPs were collected and added to a 96-well microplate (96-well microplate, polystyrene, clear, Greiner Bio-One, Cat. No.: 82050-760) for analysis using UV-Vis spectrophotometry (step size: 1 nm, number of flashes: 8, Tecan Infinite M Plex spectrophotometer). TEM samples were prepared by drop-casting the respective solutions (5 μl) onto 400 mesh pure C, Cu grids (Ted Pella, Inc., Redding, USA) and dried under hood evaporation. Prior to drop-casting, NPs were prepared via centrifugation and resuspension in MilliQ to remove residual capping agent. Prior to imaging, grids were cleaned under UV light (6 min per side). TEM images were acquired using a Hitachi HF-3300 300 kV Environmental TEM with an electron accelerating voltage of 300 kV.

[0264] 5A-5B show spectra of dye-nanoparticle (dye-NP) light blockers in solution according to embodiments of the present disclosure. 5A-5B show spectra of dye-NP light blockers in solution, showing UV-Vis spectroscopy absorbance profiles in water. FIG. 5A shows Rhodamine B dye (RhoB) and RhoB-conjugated gold nanostars (RhoB-NP) dissolved in water. FIG. 5B shows various dyes conjugated to gold nanostars with peaks spanning the target range, where "TRITC" refers to "tetramethylrhodamine isothiocyanate." All UV-Vis data for dye-NPs was collected after centrifuging samples at 12,000×g for 15 minutes to remove any excess dye until the supernatant was colorless.

[0265] Upon conjugation to gold nanostars via 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide / N-hydroxysuccinimide (EDC / NHS) click chemistry, the Rhodamine B dye retained its selective photoblocking peak with some broadening and red shift, as can be seen in Figure 5A. The photoblocking platform can also be adapted to a variety of commercially available dyes to generate tailored photoblocking profiles, as can be seen in Figure 5B.

[0266] Figure 6 shows the color profile of the dye-NP light blocker compared to existing methods according to embodiments of the present disclosure. Figure 6 shows a direct comparison of gold nanospheres blocking at the target range, RhoB dye in water, and the dye-NP combination in solution (i.e., from Figures 5A-5B). The resulting color profile for the dye-NP combination was purple (pink / red from the dye and blue from the nanostars) and was less bright and intense compared to the dye alone.

[0267] The color profile of the dye-NP light blocker compared to existing methods is shown in Figure 6. The difference in color profile between AuNP (left), dye (center), and dye-conjugated AuNP nanostars (right) is shown. The AuNP nanostars softened the bright pink color of the dye to produce a more patient-compatible purple color without sacrificing the specific light blocking of the dye.

[0268] Figures 7-10 show various absorbance spectra of nanoparticles with various surface chemistries. Nanoparticles conjugated to various rhodamine dyes were synthesized, including but not limited to rhodamine 6G, rhodamine B, tetramethylrhodamine (TRITC), and 5-carboxy-tetramethylrhodamine. These various nanoparticles could be tailored to have various full width at half maximum (FWHM) values, including but not limited to 97 nm for rhodamine 6G nanoparticles in solution (Figure 7), 70 nm for rhodamine B nanoparticles in solution (Figure 8), 118 nm for tetramethylrhodamine (TRITC) nanoparticles in solution (Figure 9), and 70 nm for 5-carboxy-tetramethylrhodamine nanoparticles in solution (Figure 10). While such results demonstrated the ability to conjugate nanoparticles to various rhodamine dyes, it should be understood that this method may be applicable to any NHS-functionalized dyes and other dyes functionalized in additional manners. Such conjugation was motivated by desired target wavelength absorption and resulted in tunable target wavelength absorption and FWHM values.

[0269] Gold nanostars conjugated to organic dyes and stabilizing mechanisms (e.g., PVP, PEG-SH, etc.) have been synthesized as described above. An exemplary process for conjugating an anchoring mechanism to gold nanostars to form nanoparticles simultaneously conjugated to organic dyes, stabilizing mechanisms, and anchoring mechanisms has been adapted from Hermanson, GT, Bioconjugate Techniques: Third Edition. Elsevier Inc. (2013) and Vu-Quang H., et al., Polymers (Basel) (2019) and is described herein. First, 10 mM rhodamine B (RhoB) (2 ml in anhydrous dimethylsulfoxide (DMSO)) is mixed with 23 μmol carbonyldiimidazole (CDI). CDI should be added directly to DMSO and not pre-dissolved. Protect the mixture from light and allow to react for >24 hours with vigorous stirring in a fume hood. As shown above, the organic dye does not have to be Rhodamine B, but can be any organic dye known in the art. Next, 200 mM polyvinyl alcohol (PVA) (5 ml in anhydrous DMSO) is added to the RhoB-CDI solution (where PVA can act as an immobilization mechanism) and the mixture is once again protected from light and allowed to react for >24 hours with vigorous stirring in a fume hood. This process conjugates RhoB with PVA via esterification using CDI as a zero-length crosslinker. The polymer does not have to be PVA, but can be any polymer and similar compound known in the art. Once the reaction is complete, the solution is dialyzed against 4 L of MilliQ water for >24 hours with repeated medium changes and then lyophilized. Now, RhoB-PVA can be used to coat gold nanoparticles (AuNPs). By introducing varying amounts of RhoB-PVA (for specific light blocking and methacrylation), additional non-functionalized PVA (for methacrylation), and PVP (for stabilization), a full complement of dyes can be generated, as well as stabilization and anchoring mechanisms, which may include methacrylation, on the same nanoparticle.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] [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 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having an emission peak that at least partially overlaps with the peak optical absorption of the plurality of gold nanoparticles; a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles. (2) The composition of embodiment 1, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm. (3) The composition of embodiment 1, wherein the base material comprises a biomaterial. (4) The composition of embodiment 1, wherein the base material comprises a biomaterial matrix. (5) The composition of embodiment 1, wherein the base material comprises a hydrogel.

[0274] (6) The composition of claim 1, wherein the base material comprises a silicone-based hydrogel. (7) The composition of embodiment 1, wherein the base material comprises a HEMA-based material. 8. The composition of claim 1, wherein at least a portion of the gold nanoparticles have a star shape. (9) The composition of embodiment 1, wherein the shape of at least a portion of the plurality of gold nanoparticles is adjusted such that the portion of the plurality of gold nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm. 10. The composition of claim 1, wherein the chemical dye comprises a rhodamine-based dye.

[0275] (11) The composition of embodiment 1, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC. (12) The composition of embodiment 1, wherein the nanoparticle coating material comprises thiolated terminal poly(ethylene glycol). 13. The composition of claim 1, wherein the nanoparticle coating material comprises poly(vinylpyrrolidone). (14) The composition of embodiment 1, wherein the shape of at least some of the gold nanoparticles is tailored to provide fluorescence quenching. (15) A method of making the composition described in embodiment 1.

[0276] (16) A composition for light filtering, said composition comprising: A base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak optical absorption value in the range of about 650 nm to about 800 nm; A chemical dye dispersed in the base material, the chemical dye having an abortion peak in the range of about 530 nm to about 560 nm; a nanoparticle coating material disposed on at least a portion of the plurality of nanoparticles. (17) The composition of embodiment 16, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm. 18. The composition of claim 16, wherein the base material comprises a biomaterial. 19. The composition of claim 16, wherein the base material comprises a biomaterial matrix. 20. The composition of claim 16, wherein the base material comprises a hydrogel.

[0277] 21. The composition of claim 16, wherein the base material comprises a HEMA-based material. 22. The composition of claim 16, wherein at least a portion of the nanoparticles have a star shape. (23) The composition of embodiment 16, wherein the shape of at least a portion of the plurality of nanoparticles is adjusted such that the portion of the plurality of nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm. 24. The composition of claim 16, wherein the chemical dye comprises a rhodamine-based dye. (25) The composition according to embodiment 16, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC.

[0278] (26) The composition of embodiment 16, wherein the nanoparticle coating material comprises thiolated terminal poly(ethylene glycol). 27. The composition of claim 16, wherein the nanoparticle coating material comprises poly(vinylpyrrolidone). (28) The composition of embodiment 16, wherein the shape of at least some of the nanoparticles is adjusted to provide fluorescence quenching. 29. The composition of claim 16, wherein the nanoparticles comprise plasmonic nanoparticles. 30. The composition of claim 16, wherein the nanoparticles comprise metal nanoparticles.

[0279] 31. The composition of claim 16, wherein the nanoparticles comprise gold nanoparticles. (32) A method for producing the composition described in embodiment 16. (33) A composition for light filtering, said composition comprising: A base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak optical absorption value in the range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having a spectral peak that is at least partially quenched by filtering the spectral curve of the nanoparticles; 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 nanoparticles. (34) The composition of embodiment 33, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm. 35. The composition of claim 33, wherein the base material comprises a biomaterial.

[0280] 36. The composition of claim 33, wherein the base material comprises a biomaterial matrix. 37. The composition of claim 33, wherein the base material comprises a hydrogel. 38. The composition of claim 33, wherein the base material comprises a HEMA-based material. (39) The composition of embodiment 33, wherein at least a portion of the nanoparticles have a star shape. (40) The composition of embodiment 33, wherein the shape of at least a portion of the plurality of nanoparticles is adjusted such that the portion of the plurality of nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm.

[0281] 41. The composition of claim 33, wherein the chemical dye comprises a rhodamine-based dye. (42) The composition according to embodiment 33, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC. 43. The composition of embodiment 33, wherein the fixing mechanism comprises glycidyl methacrylate. (44) The composition of embodiment 33, wherein the nanoparticle coating material comprises poly(vinyl alcohol). (45) The composition of embodiment 33, wherein the shape of at least some of the nanoparticles is adjusted to provide fluorescence quenching.

[0282] (46) The composition of embodiment 33, wherein the nanoparticles comprise plasmonic nanoparticles. 47. The composition of embodiment 33, wherein the nanoparticles comprise metal nanoparticles. (48) The composition of embodiment 33, wherein the nanoparticles comprise gold nanoparticles. (49) A method for producing the composition described in embodiment 33. (50) A contact lens that is a free radical reaction product of a reactive mixture comprising one or more silicone-containing components and one or more hydrophilic components, said contact lens having a water content of at least about 20 weight percent and an oxygen permeability of at least about 80 Barrers, said contact lens further comprising a composition for light filtering, said composition comprising: a plurality of nanoparticles dispersed in the contact lens, the plurality of nanoparticles exhibiting a peak optical absorption value in the range of about 650 nm to about 800 nm; a chemical dye dispersed in the contact lens, the chemical dye having a spectral peak that is at least partially extinguished by filtering the spectral curve of the nanoparticles; a fixation mechanism dispersed in the contact lens, the fixation mechanism comprising a methacryloyl-derived monomer; a nanoparticle coating material disposed on at least a portion of the plurality of nanoparticles.

[0283] (51) The contact lens of embodiment 50, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm. (52) The contact lens of embodiment 50, wherein at least a portion of the nanoparticles have a star shape. (53) The contact lens of embodiment 50, wherein the shape of at least a portion of the plurality of nanoparticles is adjusted such that the portion of the plurality of nanoparticles exhibits a peak optical absorption in the range of about 650 nm to about 800 nm. (54) The contact lens of embodiment 50, wherein the chemical dye comprises a rhodamine-based dye. (55) The contact lens of embodiment 50, wherein the chemical dye comprises one or more of rhodamine B, rhodamine 6G, or TRITC.

[0284] (56) The contact lens of embodiment 50, wherein the fixation mechanism comprises glycidyl methacrylate. (57) The contact lens of embodiment 50, wherein the nanoparticle coating material comprises poly(vinyl alcohol). (58) The contact lens of embodiment 50, wherein the shape of at least a portion of the nanoparticles is adjusted to provide fluorescence quenching. (59) The contact lens of embodiment 50, wherein the nanoparticles comprise plasmonic nanoparticles. (60) The contact lens of embodiment 50, wherein the nanoparticles comprise metal nanoparticles.

[0285] (61) The contact lens of embodiment 50, wherein the nanoparticles comprise gold nanoparticles.

Claims

1. A composition for light filtering, said composition comprising: A base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles being gold nanoparticles, the plurality of gold nanoparticles exhibiting a peak optical absorption in the range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having an emission peak that at least partially overlaps with the peak optical absorption of the plurality of gold nanoparticles; a nanoparticle coating material disposed on at least a portion of the plurality of gold nanoparticles.

2. A composition for light filtering, comprising: A base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak optical absorption in the range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having an absorption peak in the range of about 530 nm to about 560 nm; a nanoparticle coating material disposed on at least a portion of the plurality of nanoparticles.

3. A composition for light filtering, said composition comprising: A base material; a plurality of nanoparticles dispersed in the base material, the plurality of nanoparticles exhibiting a peak optical absorption in the range of about 650 nm to about 800 nm; a chemical dye dispersed in the base material, the chemical dye having a spectral peak that is at least partially extinguished by filtering a spectral curve of the plurality of nanoparticles; 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 nanoparticles.

4. 4. The composition of claim 1, wherein the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 118 nm.

5. The base material is a) a biomaterial, or b) a biomaterial matrix, or c) a hydrogel, or d) HEMA-based materials; The composition of any one of claims 1 to 3, comprising:

6. The composition of claim 1 , wherein the base material comprises a silicone-based hydrogel.

7. The composition of claim 1 , wherein at least a portion of the plurality of nanoparticles have a star shape.

8. The shape of at least some of the nanoparticles is a) the portion of the plurality of nanoparticles is tuned to exhibit a peak optical absorption in the range of about 650 nm to about 800 nm; or b) a composition according to any one of claims 1 to 3, adapted to provide fluorescence quenching.

9. The chemical dye is a) rhodamine-based dyes, or b) one or more of rhodamine B, rhodamine 6G, or TRITC; The composition of any one of claims 1 to 3, comprising:

10. the nanoparticle coating material is a) thiolated terminal poly(ethylene glycol), or b) poly(vinylpyrrolidone); 3. The composition of claim 1 or 2, comprising:

11. The composition of claim 3, wherein the nanoparticle coating material comprises poly(vinyl alcohol).

12. The nanoparticles comprising: a) plasmonic nanoparticles, or b) metal nanoparticles, or c) gold nanoparticles; The composition of any one of claims 2 to 3, comprising:

13. The composition described in claim 3, wherein the fixing mechanism includes glycidyl methacrylate.

14. A method of making the composition of any one of claims 1 to 3.

15. A contact lens comprising the composition of any one of claims 1 to 3, wherein the contact lens is a free radical reaction product of a reactive mixture comprising 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.

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