Thermally stable nanoparticles and method for making same

Abstract

1. A composition for light filtering, the composition comprising: a base material; a plurality of nanoparticles dispersed in the base material, at least a portion of the plurality of nanoparticles having an anisotropic shape; and a stabilizing mechanism configured to selectively bind to at least a portion of the plurality of nanoparticles to enhance stability of at least a portion of the plurality of nanoparticles in the base material, the stabilizing mechanism having a molecular weight selected to control thermal reshaping of the anisotropic shape of at least a portion of the plurality of nanoparticles; wherein the composition exhibits a peak optical absorption value in the range of about 600 nm to about 1000 nm, and the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 17 / 661,109, filed April 28, 2022, which is incorporated by reference in its entirety.

[0002] FIELD OF THEINVENTION FIELD OF THE DISCLOSURE This application relates generally to methods of stabilizing nanoparticles. More specifically, this application relates to coating nanoparticles to provide colloidal and thermal stability. [Background technology]

[0003] Due to their unique optical properties, chemical stability, tunability, and high surface area-to-volume ratio, metal nanoparticles represent desirable materials for biomedical applications such as sensing organs, wound dressings, and other therapeutic agents (Clasky, et al., 2021).

[0004] Research into the thermal reshaping of nanoparticles exists primarily in academia and focuses on rod-shaped nanoparticles (i.e., nanorods). Existing strategies include coating nanorods with carbon (Khalavka, et al., Journal of Physical Chemistry C, 2007), graphene oxide (Shirshani, et al., Plasmonics, 2018), gelatin (Campean, et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013), and silica (Chen, et al., Optics Express, 2010). Such strategies have been shown to be capable of limited thermal reshaping at high temperatures.

[0005] Studies focusing on the thermal reshaping of nanorods include polymer coating strategies. Recent studies have coated nanorods with poly(styrenesulfonate), poly(ethylene glycol) (PEG), poly(vinylpyrrolidone) (PVP), and phosphatidylcholine (PC) (Horiguchi, et al., 2008). This work shows that a passivation layer on the surface of the nanorods affects the nanoparticle reshaping kinetics.

[0006] A recent publication investigates the thermal reshaping of gold nanorods in a polymer matrix (Kennedy, et al., ACS Applied Materials and Interfaces, 2018). The authors embed the nanorods in a matrix of poly(methylmethacrylate) (PMMA) and apply elevated temperatures to determine their effect on reshaping. The reshaping of the nanorods was shown to be influenced by the surrounding environment, which plays an important role in slowing down surface diffusion and stabilizing the nanorod shape.

[0007] An investigation into the colloidal stability of nanoparticles found that PEGylation could be effective in stabilizing nanoparticles during autoclaving (Masse, et al., Molecules, 2019). However, this paper only deals with spherical nanoparticles, as opposed to anisotropic particles. This paper further does not address the issue of thermal reshaping.

[0008] A recent publication (Salih et al, ACS Nano 2021) demonstrates the addition of nanoparticles to contact lens materials prior to lens curing, but only uses commercially available citrate-coated gold nanoparticles. The gold nanoparticles used in this study are spherical and represent the most thermodynamically stable product of gold nanocrystals (i.e., the morphology that maximally minimizes surface energy). The integration strategy of this study (i.e., citrate coating) cannot be extended to anisotropic nanoparticles due to high surface energy and thermal reshaping.

[0009] However, improvements to the prior art tools are needed. Summary of the Invention [Means for solving the problem]

[0010] Disclosed herein are systems, compositions, and methods for improving the stability of nanoparticles in a base material.

[0011] One general embodiment includes a composition for light filtering, the composition also comprising a base material, a plurality of gold nanoparticles dispersed in the base material, at least a portion of the plurality of gold nanoparticles having an anisotropic shape, and a stabilization mechanism arranged to selectively bind to at least a portion of the plurality of gold nanoparticles to enhance stability of at least a portion of the plurality of gold nanoparticles in the base material, the molecular weight of the stabilization mechanism being selected to control thermal reshaping of the anisotropic shape of at least a portion of the plurality of gold nanoparticles, the composition exhibiting a peak optical absorption value in the range of about 600 nm to about 1000 nm, and the composition exhibiting an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm.

[0012] One general embodiment includes a composition for light filtering, the composition also comprising a base material, a plurality of nanoparticles dispersed in the base material, at least a portion of the plurality of nanoparticles having an anisotropic shape, and a stabilization mechanism arranged to selectively bind to at least a portion of the plurality of nanoparticles to enhance stability of at least a portion of the plurality of nanoparticles in the base material, the molecular weight of the stabilization mechanism being selected to control thermal reshaping of the anisotropic shape of at least a portion of the plurality of nanoparticles, the composition exhibiting a peak optical absorption value in the range of about 600 nm to about 1000 nm, and the composition exhibiting an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm.

[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 shows the absorbance spectrum of bipyramidal nanoparticles (NPs) coated with 55 kDa (S). [Figure 1B] 1 shows the absorbance spectrum of bipyramidal nanoparticles (NPs) coated with 360 kDa (M). [Figure 1C] Figure 2 shows the absorbance spectrum of 1300 kDa (L) poly(vinylpyrrolidone (PVP)-coated bipyramidal nanoparticles (NPs) after autoclaving. [Figure 2A]1 shows the absorbance spectrum of nanorod NPs coated with cetyltrimethylammonium bromide (CTAB). [Figure 2B] FIG. 1 shows the absorbance spectrum of 55 kDa coated nanorod NPs. [Figure 2C] Figure 1 shows the absorbance spectra of nanorod NPs coated with 1300 kDa PVP before and after autoclaving. The dashed line shows the spectrum before autoclaving, and the solid line shows the spectrum after autoclaving. Sample code: C = CTAB, L = low molecular weight PVP (55 kDa), H = high molecular weight PVP (1300 kDa). "-A" indicates "autoclaved". DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] There is a need to develop strategies that resist or limit thermal reshaping of nanoparticles by mitigating surface diffusion of atoms, are versatile and biocompatible for integration into various applications, and are repeatable and commercially viable for easy adoption into existing manufacturing strategies.

[0016] Furthermore, sterilization procedures can result in rearrangement of the surface atoms of nanoparticles (NPs) to lower energy configurations in a process called thermal reshaping. As a non-limiting example, sterilization procedures can include autoclaving. Such rearrangement can result in the shape of a sphere, which is more thermodynamically stable. This rearrangement can occur in anisotropic nanoparticles, such as rods or bipyramids, which revert to a spherical or icosahedral shape upon autoclaving. This process can change the properties of the nanoparticles. Such property changes can serve to defeat efforts to engineer desired nanoparticle morphologies. In addition to being able to survive autoclaving, the stability of nanoparticles at high temperatures is crucial for work in catalysis, plasmonics, photothermal therapy, and other such related applications.

[0017] To effectively utilize metal nanoparticles in these myriad applications, such nanoparticles must be able to withstand multiple stress factors, including, but not limited to, thermal and mechanical stress factors. Autoclaving may refer to a sterilization procedure that utilizes high levels of stress for an extended period of time. The stress may include thermal stress or mechanical stress. Thermal stress may result from elevated temperatures. Mechanical stress may result from elevated pressures. Extended periods may include a range of about 15 minutes up to about 60 minutes, although longer or shorter periods may be used. As non-limiting examples, extended periods may range from about 20 minutes up to about 60 minutes, about 25 minutes up to about 60 minutes, about 30 minutes up to about 60 minutes, about 35 minutes up to about 60 minutes, about 40 minutes up to about 60 minutes, about 45 minutes up to about 60 minutes, about 50 minutes up to about 60 minutes, or about 55 minutes up to about 60 minutes. Elevated temperatures may range from about 20° C. up to about 130° C., although other temperatures may be applied. As non-limiting examples, the elevated temperature can range from about 20° C. up to about 130° C., from about 30° C. up to about 130° C., from about 40° C. up to about 130° C., from about 50° C. up to about 130° C., from about 60° C. up to about 130° C., from about 70° C. up to about 130° C., from about 80° C. up to about 130° C., from about 90° C. up to about 130° C., from about 100° C. up to about 130° C., or from about 110° C. up to about 130° C. The elevated pressure can include pressures of about 290 kPa or greater, although other pressures may be used. As non-limiting examples, high pressures can include pressures of about 290 kPa up to about 360 kPa, 300 kPa up to about 360 kPa, 310 kPa up to about 360 kPa, 320 kPa up to about 360 kPa, 330 kPa up to about 360 kPa, 340 kPa up to about 360 kPa, or 350 kPa up to about 360 kPa. Due to the high surface energy, the melting points of nano-sized particles are significantly lower than their bulk counterparts.

[0018] The following disclosure relates to strategies by which thermal reshaping of nanoparticles in high stress processes can be limited. Such nanoparticles can be anisotropic. Such strategies can include coating nanoparticles. Such strategies can include adapting the viscosity of the coating rather than simply replacing the coating material. The disclosure relates to methods that use the basic strategy of coating layers to increase the viscosity at the interface. Such interfaces can include nanoparticle-polymer interfaces. The increased viscosity at the interface can result in limited thermal reshaping. High stress can include mechanical stress (e.g., pressure), thermal stress, and other such known stress factors. High stress processes can include autoclaving, sterilization procedures, and other such known processes. The disclosure further relates to both colloidal nanoparticles and gel-integrated nanoparticles. Such nanoparticles can include either rod or bipyramid shapes, although a wider variety of shapes are possible that are integrated into a wider variety of applications. The disclosure relates to a wide variety of methods for nanoparticle integration into various applications.

[0019] The present disclosure relates to nanoparticles such as metal nanoparticles, specifically gold nanoparticles. Reference to gold nanoparticles may apply to other nanoparticles, including metal nanoparticles. Gold nanoparticles may include anisotropic shapes. Anisotropic gold nanoparticles may include bipyramidal shapes, although other anisotropic shapes are possible. The present disclosure further relates to stabilization mechanisms. The use of stabilization mechanisms may enable resistance of nanoparticles to thermal stress factors. Such resistance may be enabled by passivating atoms on the surface of the nanoparticle. Passivation may limit the tendency of nanoparticle surface atoms to return to a sphere (a more thermodynamically stable conformation) under applied stress. Such applied stress may include thermal stress, mechanical stress, and other such stress factors known in the art. The present disclosure relates to stabilization mechanisms. Stabilization mechanisms may artificially increase the coordination number of nanoparticle surface atoms (e.g., creating Au-polymer bonds with Au atoms at free nanoparticle surfaces). Stabilization mechanisms may further increase the localized viscosity at the nanoparticle surface. Such surfaces may include interfaces, which may further include nanoparticle-polymer interfaces. The combination of increased coordination number and increased local viscosity may facilitate the restriction of nanoparticle surface atom movement. Such restriction may maintain nanoparticle morphology even under increased applied stress. In one aspect of the present disclosure, such increased applied stress may occur during autoclaving. Thus, the autoclave stability of gel-integrated nanoparticles may be increased.

[0020] The present disclosure relates to methods of producing nanoparticles, such as gold nanoparticles. The present disclosure further relates to methods of engineering the shape of nanoparticles. Such shape engineering can facilitate blocking of specific light ranges ranging from about 600 nm up to about 1000 nm. Engineering the nanoparticle shape can result in anisotropic gold nanoparticles. Anisotropic gold nanoparticles can include bipyramidal shapes, although other anisotropic shapes are possible. Such particles can have sharp features. The higher surface energy associated with the sharper features of anisotropic gold particles can result in thermal reshaping at high temperatures. This reshaping can result from diffusion of surface atoms to lower energy configurations. This reshaping can further require additional nanoparticle modifications to impart thermal stability. The present disclosure relates to such modifications, which overcome significant barriers to commercialization.

[0021] As a non-limiting example, thermal reshaping has been shown to depend on the aspect ratio of rod-shaped nanoparticles due to the tendency of gold atoms at the ends of the rods to diffuse to the center under various stress factors (e.g., thermal stress, mechanical stress, etc.). At high aspect ratios, there is also the threat of Rayleigh instability, which can facilitate the breakup of nanorods into chains of nanospheres. This can be due to the increase in surface tension upon reshaping.

[0022] The present disclosure relates to coated nanoparticles. Such nanoparticles may exhibit photophysical properties. The coated nanoparticles may facilitate increased stability of the nanoparticles. The nanoparticles may be integrated into optically transparent substrates as tunable optical filters to produce devices. The devices may include ophthalmic devices. However, the nanoparticles may be integrated into other devices.

[0023] The present disclosure relates to stabilization mechanisms. As a non-limiting example, the stabilization mechanism may include poly(vinylpyrrolidone) (PVP) polymer chains. Such polymer chains may include a range of molecular weights. Non-limiting examples of ranges may include molecular weights from about 55 kDa up to about 1300 kDa. Additional molecular weight ranges exist. As non-limiting examples, the molecular weight range may include about 55 kDa up to about 1200 kDa, about 55 kDa up to about 1100 kDa, about 55 kDa up to about 1000 kDa, about 55 kDa up to about 900 kDa, about 55 kDa up to about 800 kDa, about 55 kDa up to about 700 kDa, about 55 kDa up to about 600 kDa, about 55 kDa up to about 500 kDa, about 55 kDa up to about 400 kDa, about 55 kDa up to about 300 kDa, about 55 kDa up to about 200 kDa, or about 55 kDa up to about 1000 kDa. The monomer unit of PVP includes a nitrogen atom having a lone pair of electrons. Such lone pair of electrons may be attached to the surface of the gold nanoparticle. Such binding may improve colloidal stability. PVP may be bound to the nanoparticle surface by incubating the nanoparticles in a highly concentrated solution of PVP. Such a solution may contain ethanol (10-20% w / v) with a small amount of sodium dodecyl sulfate (0.6% w / v in water). Incubation may occur at 40°C overnight. The increase in the molecular weight of PVP bound to the nanoparticle surface may facilitate a reduction in thermal reshaping. The reduction in thermal reshaping may be measured by an observed change in the localized surface plasmon resonance peak.

[0024] The present disclosure relates to a method of using a stabilization mechanism of increased molecular weight. Such a stabilization mechanism may include PVP, but other stabilization mechanisms known in the art may be used. The method of using an increased molecular weight of the stabilization mechanism may result in an increased viscosity at the nanoparticle-polymer surface. The increased viscosity at the nanoparticle-polymer surface may limit the movement of surface atoms and improve the thermal stability of the nanoparticle.

[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. The present disclosure further relates to nanoparticles. Such nanoparticles may include gold. Gold nanoparticles may be grown from penta-twinned gold seeds, although other synthesis methods are known in the art. Such nanoparticles may include shapes. Such shapes may be anisotropic. Such shapes may be bipyramidal. 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 complex square prism shapes, or truncated double tetrahedron shapes. The present disclosure further relates to stabilization mechanisms. Such stabilization mechanisms may include polymers. Such polymers may include various molecular weights. Such polymers may include PVP. 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 stabilizing 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 compositions in which a base material comprising nanoparticles and a stabilization mechanism exhibits a peak optical absorption in the range of about 600 nm up to about 1000 nm.Such peak optical absorption can be tuned through adjusting the nanoparticle morphology. The morphology can be tuned by configuring the aspect ratio, defined by the quotient of the major and minor axis lengths, the volume, the sharpness, and / or other related characteristics. The aspect ratio can 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. The volume is about 250 nm. 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. 30,000nm 3 , about 9,250nm 3 ~Maximum approx. 30,000nm 3 , about 10,250nm 3 ~Maximum approx. 30,000nm 3 , about 11,250nm 3 ~Maximum approx. 30,000nm 3, about 12,250nm 3 ~Maximum approx. 30,000nm 3 , about 13,250nm 3 ~Maximum approx. 30,000nm 3 , about 14,250nm 3 ~Maximum approx. 30,000nm 3 , about 15,250nm 3 ~Maximum approx. 30,000nm 3 , about 16,250nm 3 ~Maximum approx. 30,000nm 3 , about 17,250nm 3 ~Maximum approx. 30,000nm 3 , about 18,250nm 3 ~Maximum approx. 30,000nm 3 , about 19,250nm 3 ~Maximum approx. 30,000nm 3 , about 20,250nm 3 ~Maximum approx. 30,000nm 3 , about 21,250nm 3 ~Maximum approx. 30,000nm 3 , about 22,250nm 3 ~Maximum approx. 30,000nm 3 , about 23,250nm 3 ~Maximum approx. 30,000nm 3 , about 24,250nm 3 ~Maximum approx. 30,000nm 3 , about 25,250nm 3 ~Maximum approx. 30,000nm 3 , about 26,250nm 3 ~Maximum approx. 30,000nm 3 , about 27,250nm 3 ~Maximum approx. 30,000nm 3 , about 28,250nm 3 ~Maximum approx. 30,000nm 3 , or about 29,250 nm 3 ~Maximum approx. 30,000nm 3Such adjustments may result in a Full-Width at Half Maximum (FWHM) value of about 58 nm up to about 70 nm. As non-limiting examples, the FWHM value may be in the range of about 59 nm up to about 70 nm, about 60 nm up to about 70 nm, about 61 nm up to about 70 nm, about 62 nm up to about 70 nm, about 63 nm up to about 70 nm, about 64 nm up to about 70 nm, about 65 nm up to about 70 nm, about 66 nm up to about 70 nm, about 67 nm up to about 70 nm, about 68 nm up to about 70 nm, or about 69 nm up to about 70 nm.

[0026] There are further capabilities associated with the present disclosure. The present disclosure further relates to various polymers and other such compounds known in the art that can be grafted onto the surface of nanoparticles. The use of various polymers and other such compounds can allow the integration of 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).

[0027] The present disclosure may also relate to methods of using biocompatible and gel compatible materials to limit thermal reshaping.

[0028] 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.

[0029] The following definitions are provided for terms used in this disclosure.

[0030] 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.

[0031] As used herein, the term "(meth)" refers to optional methyl substitution. Thus, terms such as "(meth)acrylate" refer to both methacrylate and acrylate.

[0032] The term "individual" includes humans and vertebrate animals.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] As used herein, "antimicrobial" means intended to kill or reduce the harmful effects of bacteria.

[0039] 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 can be adsorbed or chemically bonded to the surface of the particles suspended in the colloid, or the polymer can 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 sedimentation. Sedimentation results in the falling of particles from the colloid. Polymers adsorbed or chemically bonded to a particle can affect its colloidal stability.

[0040] 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.

[0041] "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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] A "polymer" is an organic compound having a number average molecular weight greater than 1500 and may be reactive or non-reactive.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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), and poly(methyl methacrylate) (PMMA), as well as copolymers or blends thereof, and other polymers known in the art.

[0051] 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.

[0052] 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.

[0053] A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of compositionally distinct blocks or segments. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb or graft copolymer" is made from at least one macromer.

[0054] A "repeating unit" is the smallest grouping of atoms within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0055] 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.

[0056] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can be further reacted to form a polymer.

[0057] 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.

[0058] "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).

[0059] "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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0066] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0067] 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-.

[0068] "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-.

[0069] "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.

[0070] "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.

[0071] "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.

[0072] "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.

[0073] "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.

[0074] "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-.

[0075] "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.

[0076] 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.

[0077] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Thus, for example, a siloxanyl group refers to a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanyl compound refers to a compound having at least one Si-O-Si group. "Siloxanyl" refers to monomeric (e.g., Si-O-Si) as well as oligomeric / polymeric structures (e.g., -[Si-O] n (wherein n is 2 or 3 or more). Each silicon atom in the siloxanyl group is independently selected to complete their valence. A Group(R A is replaced by (as defined in options (b) to (i) of Formula A).

[0078] "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.

[0079] "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).

[0080] "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-.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] As used herein, "immobilization" or "immobilization mechanism" refers to a process by which nanoparticles can be embedded in a polymer matrix. "Immobilization" can occur either chemically, via crosslinking of the nanoparticles to members of the exemplary matrix, or physically, via entanglement of molecules bound to the surface of the nanoparticles with members of the exemplary matrix.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] "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)).

[0092] As used herein, the term "light blocking profile" or "light blocking spectrum" refers to the absorption spectrum of a light blocking material.

[0093] The terms "red light blocking" or "red light absorbing" or "red light filtering" refer to the ability of certain particles to absorb, scatter, and / or extinguish incident light in the red region of the visible spectrum (e.g., 620-750 nm or about 600 nm up to about 850 nm). Thus, the terms "red light blocking" or "red light absorbing" encompass particles that absorb, scatter, and / or extinguish incident light in the red 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 red light blocking at one or more wavelengths or ranges of wavelengths within the spectral region.

[0094] As used herein, "nanoparticle (NP)" refers to a particle having at least one dimension that is less than 100 nm. In some cases, a nanoparticle may have at least one dimension that is less than 50 nm. NPs may have a variety of shapes. In some cases, NPs may have a cubic, spherical, rod-shaped, bipyramidal, octahedral, decahedral, cuboctahedral, tetrahedral, rhombic dodecahedral, truncated bisquare prism, or truncated double tetrahedral shape. As used herein, "plasmonic nanoparticle" refers to a metal nanoparticle that has unique optical properties due to localized surface plasmon resonance that allows it to interact with light waves. These properties can be tuned by varying the shape, size, composition, or medium surrounding the surface of the nanoparticle. It will be understood that the term includes all plasmonic nanoparticles of various shapes that will result in surface plasmon absorption and scattering spectra.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] As used herein, a "plasmonic light blocker" refers to a material that has the ability to absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum due to surface plasmon resonance (SPR) or localized surface plasmon resonance (LSPR), where the wavelength or range of wavelengths blocked corresponds to the wavelength of incident light that induces the SPR or LSPR. Thus, the term "plasmonic light blocker" encompasses particles that absorb, scatter, and / or extinguish incident light in a given region of the electromagnetic spectrum due to SPR or LSPR. The particles may be incorporated in various amounts into an optically transparent substrate to achieve an optically transparent material that exhibits a desired level of light filtering at one or more wavelengths or ranges of wavelengths in the electromagnetic spectrum. The percent blocking at a particular wavelength can be determined from the transmission spectrum of the material (blocking percentage=100-percent transmission (%T)).

[0102] 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.

[0103] 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).

[0104] 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.

[0105] 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%.

[0106] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0107] 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).

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] Formula A. The silicone-containing component may include one or more polymerizable compounds of formula A:

[0116] [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.

[0117] 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.

[0118] Formula B. The silicone-containing component of formula A may be a monofunctional polymerizable compound of formula B:

[0119] [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 12 cyclic alkoxy, alkoxy-alkyleneoxy-alkyl, aryl (e.g., phenyl), aryl-alkyl (e.g., benzyl), haloalkyl (e.g., partially or fully fluorinated alkyl), siloxy, fluoro, or combinations thereof, wherein each alkyl 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.

[0120] 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.

[0121] 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.

[0122] B-3. ​​Compounds of formula B, B-1, and B-2 may include compounds of formula B-3, wherein R A1 , R A2 , R A3 , and R A4 is independently, at each occurrence, C1-C6 alkyl or siloxy. Preferred alkyl is C1-C3 alkyl, or more preferably methyl. Preferred siloxy is trimethylsiloxy.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] B-7. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, and B-6 may include compounds of formula B-7, wherein R A6 is 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.

[0127] 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.

[0128] When Rg is (meth)acrylamide, the nitrogen group is R A9 and R A9is 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).

[0129] 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.

[0130] 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).

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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-.

[0137] 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-.

[0138] 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 may function as crosslinkers.

[0139] 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-.

[0140] 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-.

[0141] 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-.

[0142] 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:

[0143] [ka] During the ceremony, R A8 is hydrogen or methyl, Z is O, S, or N(R A9 ) and L, j1, j2, R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A9 is as defined in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0144] C-1. Compounds of formula C may include (meth)acrylates of formula C-1, which are compounds of formula C where Z is O.

[0145] 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.

[0146] 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. A9Further examples include -(CH2)3-Si(Me)(SiMe3)2 and -(CH2)3-Si(Me2)-[O-SiMe2] 1-10 -CH3 is an example.

[0147] Formula D. Compounds of formula C may include compounds of formula D:

[0148] [ka] During the ceremony, R A8 is hydrogen or methyl, Z 1 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.).

[0149] 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.

[0150] 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. 1is 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-.

[0151] D-3. Compounds of formula D, D-1, and D-2 may include compounds of formula D-3, wherein Z 1 is O.

[0152] D-4. Compounds of formula D, D-1, and D-2 may include compounds of formula D-4, wherein Z 1 N(R A9 ) and R A9 is H.

[0153] 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-.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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).

[0158] 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:

[0159] [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.

[0160] E-1. Compounds of formula E may include compounds of formula E-1, wherein Rg and Rg 1 are compounds of formula E, which are vinyl carbonates of the structure CH2=CH-OC(=O)-O- or CH2=C(CH3)-OC(=O)-O-, respectively.

[0161] E-2. Compounds of formula E may include compounds of formula E-2, wherein Rg and Rg 1 are each (meth)acrylates.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in the table below. When a compound in the table below contains a polysiloxane group, the number of Si repeat units in such a compound is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0170] [Table 1-1]

[0171] [Table 1-2]

[0172] 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.

[0173] [Table 2-1]

[0174] [Table 2-2]

[0175] The silicone-containing component can have an average molecular weight of about 400 to about 4000 Daltons.

[0176] 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.

[0177] 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.

[0178] Examples of suitable acyclic polyamides include polymers and copolymers comprising repeat units of formulae G1 and G2,

[0179] [ka] In the formula, X is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is a C1-C3 alkyl group, R 40 is selected from H, linear or branched, substituted or unsubstituted C1-C4 alkyl groups, R 41is 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 43 The number of carbon atoms in R is 8 or less in total, including 7, 6, 5, 4, 3, or fewer. 40 and R 41 The total number of carbon atoms in R may be 6 or less, or 4 or less. 42 and R 43 The total number of carbon atoms in the alkyl group may be up to 6. As used herein, a substituted alkyl group includes an alkyl group substituted with an amine group, an amide group, an ether group, a hydroxyl group, a carbonyl group, or a carboxyl group, or a combination thereof.

[0180] 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.

[0181] 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.

[0182] [ka]

[0183] 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:

[0184] [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 46is 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).

[0185] 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.

[0186] 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).

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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

[0198] With respect to ionic silicone hydrogels, the following properties (in addition to those mentioned above) may also be preferred: Lysozyme uptake (μg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 or less EXAMPLES

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

[0200] Aspect 1: A composition for light filtering, the composition comprising: a base material; a plurality of gold nanoparticles dispersed in the base material, at least a portion of the plurality of gold nanoparticles having an anisotropic shape; and a stabilization mechanism disposed to selectively bind to at least a portion of the plurality of gold nanoparticles to enhance stability of at least a portion of the plurality of gold nanoparticles in the base material, the stabilization mechanism having a molecular weight selected to control thermal reshaping of the anisotropic shape of at least a portion of the plurality of gold nanoparticles; wherein the composition exhibits a peak optical absorption value in the range of about 600 nm to about 1000 nm, and the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm.

[0201] Aspect 2: The composition of aspect 1, wherein an article formed from the composition exhibits stability after autoclaving.

[0202] Embodiment 3: The composition according to any one of embodiments 1 to 2, wherein the base material comprises a biological material.

[0203] Embodiment 4: The composition according to any one of embodiments 1 to 2, wherein the base material comprises a biomaterial matrix.

[0204] Embodiment 5: The composition of any one of embodiments 1 to 2, wherein the base material comprises a hydrogel.

[0205] Example 6: The composition of any one of Examples 1-5, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned gold seeds.

[0206] Embodiment 7: The composition of any one of embodiments 1-6, wherein at least a portion of the plurality of gold nanoparticles have a bipyramidal shape.

[0207] Aspect 8: The composition of aspect 7, wherein the sharpness of the bipyramidal shape is adjusted such that the composition exhibits a peak optical absorbance in the range of about 600 nm to about 1000 nm.

[0208] Embodiment 9: The composition of any one of embodiments 1-8, wherein at least a portion of the plurality of gold nanoparticles each have a pair of opposing truncated peaks disposed at opposing ends.

[0209] Embodiment 10: The composition of embodiment 9, wherein the sharpness of the bipyramidal shape is adjusted such that the composition has a peak optical absorption in the range of about 600 nm to about 1000 nm.

[0210] Embodiment 11: The composition of any one of embodiments 1 to 10, wherein the stabilization mechanism comprises poly(vinylpyrrolidone).

[0211] Embodiment 12: The composition according to any one of embodiments 1 to 10, wherein the stabilization mechanism comprises 55 kDa poly(vinylpyrrolidone).

[0212] Embodiment 13: The composition according to any one of embodiments 1 to 10, wherein the stabilization mechanism comprises 360 kDa poly(vinylpyrrolidone).

[0213] Embodiment 14: The composition according to any one of embodiments 1 to 10, wherein the stabilization mechanism comprises 1300 kDa poly(vinylpyrrolidone).

[0214] Aspect 15: The composition of any one of aspects 1 to 14, wherein the stabilization mechanism enhances colloidal stability, thermal stability, or both of at least a portion of the plurality of gold nanoparticles in the base material.

[0215] Aspect 16: A composition described in any one of aspects 1 to 15, wherein the stabilization mechanism enhances the biocompatibility of at least a portion of the multiple gold nanoparticles in the base material.

[0216] Aspect 17: A composition described in any one of aspects 1 to 16, wherein the stabilization mechanism chemically bonds to at least a portion of the plurality of gold nanoparticles to improve the stability of at least a portion of the plurality of gold nanoparticles in the base material.

[0217] Embodiment 18: The composition of embodiment 17, wherein the stabilization mechanism enhances thermal stability.

[0218] Example 19: The composition of example 17, wherein the stabilization mechanism enhances colloidal stability, thermal stability, or both of at least a portion of the plurality of gold nanoparticles in the base material.

[0219] Example 20: The composition of example 17, wherein the stabilization mechanism enhances the biocompatibility of at least a portion of the multiple gold nanoparticles in the base material.

[0220] Embodiment 21: A method of making a composition according to any one of embodiments 1 to 20.

[0221] Example 22: The method of example 21, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned gold seeds.

[0222] Aspect 23: A composition for light filtering, the composition comprising: a base material; a plurality of nanoparticles dispersed in the base material, at least a portion of the plurality of nanoparticles having an anisotropic shape; and a stabilization mechanism arranged to selectively bind to at least a portion of the plurality of nanoparticles to enhance stability of at least a portion of the plurality of nanoparticles in the base material, the stabilization mechanism having a molecular weight selected to control thermal reshaping of the anisotropic shape of at least a portion of the plurality of nanoparticles; wherein the composition exhibits a peak optical absorption value in the range of about 600 nm to about 1000 nm, and the composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm.

[0223]

[0041] Example 24: The composition of example 23, wherein an article formed from the composition exhibits stability after autoclaving.

[0224] Embodiment 25: The composition according to any one of embodiments 23 to 24, wherein the base material comprises a biological material.

[0225] Embodiment 26: The composition according to any one of embodiments 23 to 24, wherein the base material comprises a biomaterial matrix.

[0226] Embodiment 27: The composition according to any one of embodiments 23 to 24, wherein the base material comprises a hydrogel.

[0227] Embodiment 28: The composition of any one of embodiments 23-24, wherein at least a portion of the plurality of nanoparticles have a bipyramidal shape.

[0228] Example 29: The composition of example 28, wherein the sharpness of the bipyramidal shape is adjusted such that the composition exhibits a peak optical absorbance in the range of about 600 nm to about 1000 nm.

[0229] Embodiment 30: The composition of any one of embodiments 23-29, wherein at least a portion of the plurality of nanoparticles each have a pair of opposing truncated peaks disposed at opposing ends.

[0230] Aspect 31: The composition of aspect 30, wherein the sharpness of the bipyramidal shape is adjusted such that the composition has a peak optical absorption in the range of about 600 nm to about 1000 nm.

[0231] Embodiment 32: The composition of any one of embodiments 23 to 31, wherein the stabilization mechanism comprises poly(vinylpyrrolidone).

[0232] Embodiment 33: The composition according to any one of embodiments 23 to 31, wherein the stabilization mechanism comprises 55 kDa poly(vinylpyrrolidone).

[0233] Embodiment 34: The composition according to any one of embodiments 23 to 31, wherein the stabilization mechanism comprises 360 kDa poly(vinylpyrrolidone).

[0234] Embodiment 35: The composition according to any one of embodiments 23 to 31, wherein the stabilization mechanism comprises 1300 kDa poly(vinylpyrrolidone).

[0235] Aspect 36: The composition of any one of aspects 23 to 31, wherein the stabilization mechanism enhances the colloidal stability, the thermal stability, or both of at least a portion of the plurality of nanoparticles in the base material.

[0236] Aspect 37: A composition described in any one of aspects 23 to 36, wherein the stabilization mechanism enhances the biocompatibility of at least a portion of the multiple nanoparticles in the base material.

[0237] Aspect 38: A composition described in any one of aspects 23 to 37, wherein the stabilization mechanism chemically bonds with at least a portion of the plurality of nanoparticles to improve the stability of at least a portion of the plurality of nanoparticles in the base material.

[0238] Embodiment 39: The composition according to embodiment 38, wherein the stabilization mechanism enhances thermal stability.

[0239] Aspect 40: The composition of aspect 38, wherein the stabilization mechanism enhances the colloidal stability, the thermal stability, or both of at least a portion of the plurality of nanoparticles in the base material.

[0240] Aspect 41: A composition described in any one of aspects 23 to 40, wherein the stabilization mechanism enhances the biocompatibility of at least a portion of the multiple nanoparticles in the base material.

[0241] Example 42: The composition of any one of Examples 23 to 41, wherein the nanoparticles comprise plasmonic nanoparticles.

[0242] Example 43: The composition of any one of Examples 23 to 41, wherein the nanoparticles comprise metal nanoparticles.

[0243] Embodiment 44: A method of making a composition according to any one of embodiments 23 to 43.

[0244] Example 45: The method of example 44, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned seeds.

[0245] The phenomenon of thermal reshaping of anisotropic nanoparticles has been established (Kennedy, et al, ACS Appl. Mater. Interfaces, 2018; Cho, et al., J. Phys. Chem. C, 2020; Mohamed, et al., J. Phys. Chem. B, 1998). It has been shown that the melting point of the material is significantly reduced in the nanorange due to an increase in the proportion of high-energy surface atoms. Thus, high temperatures have been shown to induce surface diffusion and rearrangement of Au atoms into more thermodynamically stable conformations (Kennedy, et al, ACS Appl. Mater. Interfaces, 2018; Huang, et al., RSC Adv., 2014). This process resulted in a decrease in the aspect ratio and a gradual transition to a more spherical morphology. For gold nanorods, thermal stability has been shown to decrease with increasing aspect ratio, likely due to curvature-induced surface diffusion of atoms at the ends of the rods (Taylor, et al., ACS Nano, 2014). Minimizing nanoparticle reshaping at elevated temperatures has been noted as important due to the dependence of localized surface plasmon resonance (LSPR) on nanoparticle shape.

[0246] The effect of poly(vinylpyrrolidone) (PVP) molecular weight on the thermal reshaping of gold bipyramids integrated into contact lenses was examined. Bipyramids were coated with 55 kDa (Figure 1A), 360 kDa (Figure 1B), or 1300 kDa PVP (Figure 1C) and cured in an etafilcon mixture to produce contact lenses. Lenses were added to MilliQ water and autoclaved at 121 °C for 30 min. Ultraviolet-visible (UV-Vis) spectroscopy was performed before and after autoclaving to evaluate the effect on bipyramid thermal reshaping. Figures 1A-C show that increasing the molecular weight of PVP reduced the blue shift of autoclaved nanoparticles. For the molecular weights tested, the longitudinal LSPR peak blue-shifted by 60 nm (55 kDa, FIG. 1A), 56 nm (360 kDa, FIG. 1B), and 26 nm (1300 kDa, FIG. 1C), respectively, after autoclaving.

[0247] The effect of autoclaving on the colloidal stability and reshaping of gold nanorods was investigated, as shown in Figures 2A-C. Three colloidal suspensions of nanorods of different sizes / aspect ratios were synthesized and then coated with cetyltrimethylammonium bromide (CTAB) (Figure 2A), 55 kDa (Figure 2B), or 1300 kDa (Figure 2C) PVP. The solutions were autoclaved, and absorbance spectra were used to determine the extent of reshaping. All of the as-synthesized nanorods coated with CTAB (Figure 2A) reverted to a single LSPR peak after autoclaving and exhibited a spherical shape. All of the low molecular weight (55 kDa) PVP-coated nanorods (Figure 2B) fell out of solution and therefore presented a very weak and broad LSPR peak. In contrast, as shown in Figure 2C, nanorods coated with high molecular weight (1300 kDa) PVP retained both LSPR peaks and exhibited only a slight blue shift.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] [Embodiment] (1) A composition for light filtering, said composition comprising: A base material; a plurality of gold nanoparticles dispersed in the base material, at least a portion of the plurality of gold nanoparticles having an anisotropic shape; a stabilization mechanism arranged to selectively bind to at least a portion of the plurality of gold nanoparticles to enhance stability of at least the portion of the plurality of gold nanoparticles in the base material, the molecular weight of the stabilization mechanism being selected to control thermal reshaping of the anisotropic shape of at least the portion of the plurality of gold nanoparticles; the composition exhibits a peak light absorption value in the range of about 600 nm to about 1000 nm; The composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm. (2) The composition of claim 1, wherein an article formed from the composition exhibits stability after autoclaving. (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.

[0252] 6. The composition of claim 1, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned gold seeds. (7) The composition of embodiment 1, wherein at least a portion of the gold nanoparticles have a bipyramidal shape. (8) The composition of embodiment 7, wherein the sharpness of the bipyramidal shape is adjusted such that the composition exhibits a peak optical absorption in the range of about 600 nm to about 1000 nm. 9. The composition of claim 1, wherein at least a portion of the plurality of gold nanoparticles each have a pair of opposing truncated peaks disposed at opposite ends. (10) The composition of embodiment 9, wherein the sharpness of the bipyramidal shape is adjusted such that the composition has a peak optical absorption in the range of about 600 nm to about 1000 nm.

[0253] 11. The composition of claim 1, wherein the stabilizing mechanism comprises poly(vinylpyrrolidone). (12) The composition of embodiment 1, wherein the stabilization mechanism comprises 55 kDa poly(vinylpyrrolidone). (13) The composition of embodiment 1, wherein the stabilization mechanism comprises 360 kDa poly(vinylpyrrolidone). (14) The composition of embodiment 1, wherein the stabilization mechanism comprises 1300 kDa poly(vinylpyrrolidone). (15) The composition of claim 1, wherein the stabilization mechanism enhances the colloidal stability, the thermal stability, or both, of at least the portion of the plurality of gold nanoparticles in the base material.

[0254] (16) The composition of claim 1, wherein the stabilization mechanism enhances the biocompatibility of at least the portion of the plurality of gold nanoparticles in the base material. (17) The composition of claim 1, wherein the stabilization mechanism chemically bonds to at least a portion of the plurality of gold nanoparticles to enhance stability of at least the portion of the plurality of gold nanoparticles in the base material. 18. The composition of claim 17, wherein the stabilization mechanism enhances thermal stability. 19. The composition of claim 17, wherein the stabilization mechanism enhances the colloidal stability, the thermal stability, or both, of at least the portion of the plurality of gold nanoparticles in the base material. (20) The composition of embodiment 17, wherein the stabilization mechanism enhances the biocompatibility of at least the portion of the plurality of gold nanoparticles in the base material.

[0255] (21) A method of making the composition described in embodiment 1. 22. The method of claim 21, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned gold seeds. (23) A composition for light filtering, comprising: A base material; a plurality of nanoparticles dispersed in the base material, at least a portion of the plurality of nanoparticles having an anisotropic shape; a stabilization mechanism arranged to selectively bind to at least a portion of the plurality of nanoparticles to enhance stability of at least the portion of the plurality of nanoparticles in the base material, the molecular weight of the stabilization mechanism being selected to control thermal reshaping of the anisotropic shape of at least the portion of the plurality of nanoparticles; the composition exhibits a peak light absorption value in the range of about 600 nm to about 1000 nm; The composition exhibits an absorption spectrum having a full width at half maximum of about 58 nm to 70 nm. 24. The composition of claim 23, wherein an article formed from the composition exhibits stability after autoclaving. 25. The composition of claim 23, wherein the base material comprises a biomaterial.

[0256] 26. The composition of claim 23, wherein the base material comprises a biomaterial matrix. 27. The composition of claim 23, wherein the base material comprises a hydrogel. (28) The composition of embodiment 23, wherein at least a portion of the nanoparticles have a bipyramidal shape. (29) The composition of embodiment 28, wherein the sharpness of the bipyramid shape is adjusted such that the composition exhibits a peak optical absorbance in the range of about 600 nm to about 1000 nm. (30) The composition of embodiment 23, wherein at least a portion of the nanoparticles each have a pair of opposing truncated peaks disposed at opposite ends.

[0257] (31) The composition of embodiment 30, wherein the sharpness of the bipyramid shape is adjusted such that the composition has a peak optical absorption in the range of about 600 nm to about 1000 nm. 32. The composition of embodiment 23, wherein the stabilizing mechanism comprises poly(vinylpyrrolidone). (33) The composition of embodiment 23, wherein the stabilization mechanism comprises 55 kDa poly(vinylpyrrolidone). (34) The composition of embodiment 23, wherein the stabilization mechanism comprises 360 kDa poly(vinylpyrrolidone). (35) The composition of embodiment 23, wherein the stabilization mechanism comprises 1300 kDa poly(vinylpyrrolidone).

[0258] (36) The composition of embodiment 23, wherein the stabilization mechanism enhances colloidal stability, thermal stability, or both of at least the portion of the plurality of nanoparticles in the base material. (37) The composition of embodiment 23, wherein the stabilization mechanism enhances the biocompatibility of at least the portion of the plurality of nanoparticles in the base material. (38) The composition of embodiment 23, wherein the stabilization mechanism chemically bonds with at least a portion of the plurality of nanoparticles to enhance stability of at least the portion of the plurality of nanoparticles in the base material. 39. The composition of embodiment 38, wherein the stabilization mechanism improves thermal stability. (40) The composition of embodiment 38, wherein the stabilization mechanism enhances the colloidal stability, the thermal stability, or both of at least the portion of the plurality of nanoparticles in the base material.

[0259] (41) The composition of embodiment 23, wherein the stabilization mechanism enhances the biocompatibility of at least the portion of the plurality of nanoparticles in the base material. (42) The composition of embodiment 23, wherein the nanoparticles comprise plasmonic nanoparticles. 43. The composition of embodiment 23, wherein the nanoparticles comprise metal nanoparticles. (44) A method for producing the composition described in embodiment 1. 45. The method of claim 44, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned seeds.

Claims

1. A composition for light filtering, said composition comprising: A base material; a plurality of nanoparticles dispersed in the base material, at least some of the nanoparticles having an anisotropic shape; a stabilization mechanism arranged to selectively bind with at least a portion of the plurality of nanoparticles to enhance stability of at least the portion of the plurality of nanoparticles in the base material, the molecular weight of the stabilization mechanism being selected to control thermal reshaping of the anisotropic shape of at least the portion of the plurality of nanoparticles; the composition exhibits a peak light absorption value in the range of about 600 nm to about 1000 nm; the composition exhibits an absorption spectrum with a full width at half maximum of about 58 nm to 70 nm; A composition wherein the stabilization mechanism comprises poly(vinylpyrrolidone).

2. The composition described in claim 1, wherein the nanoparticles are gold nanoparticles.

3. The nanoparticles a) plasmonic nanoparticles, or b) metal nanoparticles; The composition of claim 1 comprising:

4. 3. The composition of claim 1 or 2, wherein an article formed from the composition exhibits stability after autoclaving.

5. The base material is a) a biomaterial, or b) a biomaterial matrix, or c) hydrogels, 3. The composition of claim 1 or 2, comprising:

6. 3. The composition of claim 2, wherein at least a portion of the plurality of gold nanoparticles are grown from penta-twinned gold seeds.

7. The composition of claim 1 or 2, wherein at least a portion of the nanoparticles have a bipyramidal shape.

8. The composition described in claim 7, wherein the sharpness of the bipyramidal shape is adjusted so that the composition exhibits peak light absorption in the range of about 600 nm to about 1000 nm.

9. 3. The composition of claim 1, wherein at least some of the nanoparticles each have a pair of opposing truncated peaks located at opposite ends.

10. The composition of claim 1 or 2, wherein the stabilizing mechanism comprises poly(vinylpyrrolidone) of 360 kDa to 1300 kDa.

11. 3. The composition of claim 1 or 2, wherein the stabilizing mechanism comprises 1300 kDa poly(vinylpyrrolidone).

12. The composition of claim 1 or 2, wherein the stabilization mechanism enhances colloidal stability, thermal stability, or both of at least the portion of the plurality of nanoparticles in the base material.

13. The composition of claim 1 or 2, wherein the stabilization mechanism enhances the biocompatibility of at least the portion of the plurality of nanoparticles in the base material.

14. The composition of claim 1 or 2, wherein the stabilization mechanism chemically bonds with at least a portion of the plurality of nanoparticles to enhance the stability of at least the portion of the plurality of nanoparticles in the base material.

15. A contact lens comprising the composition of any one of claims 1 to 3, 1. A contact lens, the contact lens being a free radical reaction product of a reactive mixture comprising one or more silicone-containing components and one or more hydrophilic components, the contact lens having 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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