Compositions and methods for sunscreen compounds

Abstract

Disclosed herein are methods of making and using sunscreen compositions comprising at least one UV-absorbing binding compound. The disclosure includes compositions having at least one UV-absorbing binding compound that reflects and / or absorbs UV radiation, such as UV-A, UV-B, and / or both UV-A and UV-B, and that are not absorbed by, transmitted through, and / or transported from a subject's body surface into the body or into the circulatory system of the subject's body.

Description

[Technical Field]

[0001] Related Applications This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 62 / 888,526, filed August 18, 2019, and U.S. Provisional Patent Application No. 62 / 910,902, filed October 4, 2019, each of which is incorporated herein in its entirety.

[0002] The present disclosure relates to compositions containing compounds that prevent the absorption of UV radiation, particularly for topical applications. [Background technology]

[0003] Many people are using sunscreen compositions, for example, that reflect ultraviolet (UV) radiation from external body surfaces more frequently and for longer periods of time than previously known. People apply sunscreens daily, and all age groups, from infants to the elderly, use such compositions. Previously, people only applied sunscreens during outdoor activities. The safety of sunscreen compositions has become an issue due to frequent, prolonged use by many people over many years. It was long assumed that UV-reflecting compounds were not absorbed through the skin into the body's systemic circulation. However, recent studies have shown that such compounds can be absorbed through the skin and enter the body. For example, in 2019, Matta et al. reported the results of a preliminary maximum use test (MUsT) in the Journal of the American Medical Association, studying the systemic absorption (through the skin into the body) of sunscreen active ingredients using four commercially available sunscreen products. MUsT studies evaluate the systemic absorption of topical drugs (i.e., those applied to the skin) when used at the maximum recommended doses per product's instructions. This pilot study demonstrated that all four tested active ingredients were absorbed from each test formulation, demonstrating that sunscreen absorption is not merely a theoretical concern. The U.S. Food and Drug Administration (FDA) has published a proposed rule updating regulatory requirements for many U.S. sunscreen products. Sunscreens are regulated as drugs in the United States. As part of this rule, the FDA is requesting additional safety data on 12 sunscreen active ingredients currently available in over-the-counter products because there is a lack of data on whether and to what extent the ingredients are absorbed by the body after topical application. Despite increased human use of sunscreens, the incidence of skin cancer continues to rise, and skin cancer remains the most commonly diagnosed cancer in the United States. This incidence makes the risks of excessive sun exposure a significant public health priority. Broad-spectrum sunscreens with SPF values ​​of at least 15 are needed to prevent skin cancer and protect the skin from sunburn and other UV damage. What is needed are formulation compositions, such as sunscreen formulations, that include at least one UV-absorbing conjugate that is not absorbed, transmitted, and / or transported across body surface barriers, or that is poorly absorbed, transmitted, and / or transported across body surfaces such as skin, hair, nails, and mucous membranes, or that is slowly absorbed, transmitted, and / or transported, and does not readily enter the body's systemic circulation. Summary of the Invention

[0004] The present disclosure includes compositions having at least one UV-absorbing binding compound that reflects and / or absorbs UV radiation, such as UV-A, UV-B, and / or both UV-A and UV-B, and is not absorbed by a subject's body surface, is not transmitted through the surface, and / or is not transported from the body surface into the interior of the body or into the circulatory system of the subject's body. In certain embodiments, the present disclosure discloses pharmaceutical compositions comprising benzotriazole-linked compounds, wherein the benzotriazole compound is attached to a linking compound via an amide linker, the benzotriazole compound having a molecular weight of at least 800 daltons, and the benzotriazole compound absorbs ultraviolet light; pharmaceutical compositions comprising benzotriazole-linked compounds, wherein the benzotriazole compound is attached to a linking compound via a product of a Michael addition reaction, the benzotriazole compound having a molecular weight of at least 800 daltons, and the benzotriazole compound absorbs ultraviolet light; pharmaceutical compositions comprising benzotriazole-functionalized polymers, wherein the benzotriazole compound is attached to the polymer as a methacrylate, acrylate, or acrylamide derivative of the benzotriazole compound, the benzotriazole compound absorbs ultraviolet light; and / or pharmaceutical compositions comprising benzotriazole-polysaccharide-linked compounds, wherein the benzotriazole compound is attached to a polysaccharide, the benzotriazole compound having a molecular weight of at least 800 daltons, and the benzotriazole compound absorbs ultraviolet light. In some embodiments, the UV absorbing binding compound (UV absorbing compound) has the formula (1) (UX): n -C, where U is a UV-absorbing compound moiety, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or —CO—NH—NH—CO—, C is a linking compound moiety, and n is an integer, n≧1.

[0005] In some embodiments, the UV absorbing binding compound has the structure shown in formula (2): [ka] and wherein Y is a UV-absorbing compound moiety, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n is an integer and n≧1, m and z are integers and m≧0, z≧0. The structure of formula (2) may be a block copolymer or a random copolymer. In some embodiments, the UV absorbing binding compound has the structure of formula (3): (UX) n -C-(X-U1) m (3) and In the formula, U is a UV-absorbing compound moiety, U1 is a UV-absorbing compound moiety having a chemical structure different from U, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, and n and m are each an integer, and n and m are ≧1. In some embodiments, the UV absorbing binding compound has the structure shown in formula (4): [ka] and wherein Y is a UV absorbing compound moiety, Y1 is a UV absorbing compound moiety having a chemical structure different from Y, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n and p are each integers, n and p are ≧1, m and z are each integers, m≧0, z≧0. The structure of formula (4) may be a block copolymer or a random copolymer. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 shows an exemplary UV absorbing binding compound that includes a benzotriazole acrylate UV absorbing compound and a small molecule as the binding compound. [Figure 2] FIG. 2 shows an exemplary UV absorbing binding compound that includes a benzotriazole acrylamide UV absorbing compound and a non-degradable polymer molecule as the binding compound. [Figure 3] FIG. 3 shows an exemplary UV absorbing linked compound that includes a benzotriazole acrylamide UV absorbing compound and a degradable polymer molecule as the linked compound. [Figure 4] FIG. 4 shows an exemplary UV absorbing binding compound that includes a benzotriazole acrylate UV absorbing compound and a small molecule as the binding compound. [Figure 5] FIG. 5 shows an exemplary UV absorbing binding compound that includes a benzotriazole acrylate UV absorbing compound and a polymer molecule as the binding compound. [Figure 6] FIG. 6 shows an exemplary UV absorbing combined compound that includes a benzotriazole acrylate UV absorbing compound and an absorbing / degradable molecule as the combined compound. [Figure 7] FIG. 7 shows an exemplary UV absorbing binding compound that includes a benzotriazole carboxylate UV absorbing compound and a small molecule as the binding compound. [Figure 8] FIG. 8 shows an exemplary UV absorbing binding compound that includes a benzotriazole carboxylate UV absorbing compound and a non-degradable polymer molecule as the binding compound. [Figure 9] FIG. 9 shows an exemplary UV absorbing binding compound that includes a benzotriazole carboxylate UV absorbing compound and a degradable polymer molecule as the binding compound. [Figure 10] FIG. 10 shows an exemplary UV absorbing binding compound comprising a linear polymer with a benzotriazole UV absorbing compound. [Figure 11] FIG. 11 shows an exemplary UV absorbing binding compound comprising a crosslinked polymer with a benzotriazole UV absorbing compound. [Figure 12] FIG. 12 shows an exemplary UV-absorbing binding compound that includes a UV-absorbing compound having a sulfonate group and a small molecule as the binding compound. [Figure 13] FIG. 13 shows an exemplary UV-absorbing binding compound that includes a UV-absorbing compound having a sulfonic acid and a non-degradable polymer molecule as the binding compound. [Figure 14] FIG. 14 shows an exemplary UV-absorbing binding compound that includes a UV-absorbing compound having a sulfonic acid and a degradable polymer molecule as the binding compound. [Figure 15] FIG. 15 shows an exemplary UV absorbing linked compound that includes a benzotriazole hydrazide UV absorbing compound and a small molecule as the linked compound. [Figure 16] FIG. 16 shows an exemplary UV absorbing binding compound that includes a benzotriazole hydrazide UV absorbing compound and a non-degradable polymer molecule as the binding compound. [Figure 17] FIG. 17 shows an exemplary UV absorbing linking compound that includes a benzotriazole hydrazide UV absorbing compound and a degradable polymer molecule as the linking compound. [Figure 18] FIG. 18 is a graph showing the NMR results for the UV absorbing bonded compound of Example 16. [Figure 19] FIG. 19 is a graph of the UV spectrum for the UV absorbing bonded compound of Example 16 in dichloromethane. [Figure 20] FIG. 20 is a graph showing the NMR results for the UV absorbing bonded compound of Example 18. [Figure 21] FIG. 21 is a graph of the UV spectrum for the UV absorbing bonded compound of Example 18 in dichloromethane. DETAILED DESCRIPTION OF THE INVENTION

[0007] Disclosed herein are compositions comprising at least one UV-absorbing binding compound, and methods of making and using such compositions. As used herein, a UV-absorbing compound is a compound that reflects and / or absorbs radiation in certain ultraviolet (UV) wavelengths. In certain embodiments, disclosed herein are inorganic compounds that reflect or scatter light away from the skin, and organic (carbon-based) compounds that absorb UV radiation. Some inorganic compounds, including zinc oxide or titanium dioxide, act as sunblocks for the body, preventing radiation from reaching the body surface. Examples of organic compounds that are UV-absorbing compounds include, but are not limited to, avobenzone or oxybenzone. These molecules do not physically deflect UV rays, but rather absorb UV radiation through chemical bonds. As the bonds absorb UV radiation, the sunscreen ingredients slowly break down, releasing heat. SPF is often used to describe the level of protection provided by sunscreen compositions. SPF stands for Sun Protection Factor and refers to how well a sunscreen protects against UVB rays, which can cause sunburn and some types of skin cancer. UVA radiation penetrates deeper into the skin and can cause premature wrinkling, age spots, and may also increase the risk of some skin cancers. Broad spectrum sunscreens block both UVA and UVB rays, but there are currently no standards for describing UVA absorption. Inorganic compounds that deflect sunlight deflect both UVA and UVB rays. Because sunscreen compositions higher than SPF 50 have not been proven to be more effective than SPF 50, the use of sunscreen compositions with SPFs between 15 and 50 is recommended. While no composition can block 100 percent of UV rays, an SPF 15 sunscreen protects against approximately 93% of UVB rays, and an SPF 30 protects against 97% of UV rays. Because sunscreen compositions do not filter out UV radiation that reaches the body's surface, the SPF number refers to the approximate length of time it takes for human skin to show radiation damage, such as reddening. An SPF 15 sunscreen composition prevents Caucasian skin from reddening approximately 15 times longer than skin without the sunscreen composition. For example, if skin begins to burn (redden) after 10 minutes, an SPF 15 sunscreen composition will prevent burning for approximately 150 minutes, or 2.5 hours.

[0008] Disclosed herein are pharmaceutical compositions comprising at least one UV-absorbing binding compound composition for use in preventing or ameliorating the harmful effects of UV radiation, such as from the sun, including cosmetic compositions comprising one or more compounds or molecules that reflect and / or absorb UV-A, UV-B, or both UV-A and UV-B radiation. It is desirable that the UV-absorbing binding compound not be significantly absorbed through body surfaces, such as the skin, or transported into the body's systemic circulation. The biological activity and toxicity of many currently used UV-absorbing and / or UV-reflecting compounds have not been studied. Disclosed herein are UV-absorbing binding compounds, which include a UV-absorbing compound bound to a binding compound, which can be a small molecule or a polymer. In some embodiments, the compositions disclosed herein include at least one UV-absorbing compound. The effective molecular weight is increased by binding the binding compound to the UV-absorbing compound, thereby reducing absorption of the UV-absorbing compound through the skin. In some embodiments, the effective molecular weight of the UV-absorbing compound can be increased by covalently binding the UV-absorbing compound to a binding compound or molecule (referred to herein as a UV-absorbing binding compound) such that the total molecular weight of the bound molecule is greater than 500 Daltons, greater than 800 Daltons, or greater than 1000 Daltons. For brevity, UV-absorbing binding compounds may be referred to herein as "absorbing compounds" and include compounds that absorb UV radiation, reflect UV radiation, or absorb and reflect UV radiation.

[0009] In some embodiments, the UV absorbing binding compound (UV absorbing compound) has the structure shown in formula (1): (UX) n -C (1) and wherein U is a UV absorbing compound moiety, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or —CO—NH—NH—CO—, C is a linking compound moiety, and n is an integer, n≧1. In some embodiments, the UV absorbing binding compound has the structure shown in formula (2): [ka] and In the formula, Y is a UV-absorbing compound moiety, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n is an integer and n≧1, m and z are integers and m≧0, z≧0. The structure of formula (2) may be a block copolymer or a random copolymer. In some embodiments, the UV absorbing binding compound has the structure shown in formula (3): (UX) n -C-(X-U1) m (3) and In the formula, U is a UV-absorbing compound moiety, U1 is a UV-absorbing compound moiety having a chemical structure different from U, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, and n and m are each an integer, and n and m are ≧1. In some embodiments, the UV absorbing binding compound has the structure shown in formula (4): [ka] and wherein Y is a UV absorbing compound moiety, Y1 is a UV absorbing compound moiety having a chemical structure different from Y, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n and p are each integers, n and p are ≧1, m and z are each integers, m≧0, z≧0. The structure of formula (4) may be a block copolymer or a random copolymer.

[0010] The compositions of the present disclosure may include one or more UV-absorbing binding compounds having a UV-absorbing compound bound (conjugated) to a binding compound. In some embodiments, the binding compound of the UV-absorbing binding compound is not a polymer-containing binding compound (described below) and has a molecular weight of less than 1000 daltons, from about 100 daltons to about 1000 daltons, from about 100 daltons to about 900 daltons, from about 200 daltons to about 8000 daltons, from about 200 daltons to about 1000 daltons, from about 100 daltons to about 300 daltons, from about 200 daltons to about 500 daltons, from about 300 daltons to about 1000 daltons; or from about 400 daltons to about 8000 daltons. The binding compound may be a small molecule having a molecular weight of about 400 to about 1000 daltons; about 500 to about 1000 daltons; about 400 to about 800 daltons, about 500 to about 600 daltons, about 600 to about 1000 daltons, about 600 to about 800 daltons, about 700 to about 1000 daltons, about 800 to about 1000 daltons, about 800 to about 900 daltons, or about 900 to about 1000 daltons, and all ranges therebetween. In some embodiments, the binding compound has one or more functional groups capable of reacting with the functional group of the UV-absorbing compound. The functional group may be a part of the binding compound or may be added to the binding group by chemical synthesis methods. The functional group of the binding compound may include, but is not limited to, one or more thiol groups, amine groups, hydrazide groups, carboxylic acid groups, or combinations thereof. In some embodiments, the binding compound may be an alkane. In some embodiments, the binding compound is a straight-chain alkane. In some embodiments, the binding compound is a branched alkane. In some embodiments, the binding compound comprises an aromatic ring. In some embodiments, the binding compound comprises a benzene ring. In some embodiments, the binding compound comprises two or more thiol or amine groups. In some embodiments, the binding compound comprises at least one thiol group and at least one amine group. In some embodiments, the amine group is a primary amine group. In some embodiments, the binding compound comprises one or more carboxylic acid groups. In some embodiments, the binding compound comprises one or more hydrazide groups.

[0011] In some embodiments, a linking compound having two or more amine groups can be reacted with one or more UV absorbing compounds having a carboxylic acid group, an acrylate group, a methacrylate group, or an acrylamide group. For example, binding compounds having two or more amine groups and which are alkanes include, but are not limited to, C2 to C20 diamines, 1,5-diamino-2-methylpentane, 1,3-diamino-2-propanol, 3,3'-diamino-N-methyldipropylamine, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, meso-1,4-diamino-2,3-butanediol dihydrochloride, 1,4-diamino-2-butanone dihydrochloride, 2,2-bis(aminoethoxy)propane, spermidine, DL-5-hydroxylysine hydrochloride, triethylenetetramine, tetraethylenepentaminecystine, diethylenetriamine, bis(3-aminopropyl)amine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 4,9-dioxa-1,12-dodecanediamine, and 2,6-diaminopimelic acid. In some embodiments, the binding compound comprising a benzene ring and at least two amine groups includes, but is not limited to, 1,2-diamino-3,5-dimethylbenzene, 4,4'-diamino[1,1'-biphenyl]-3,3'-diol, 1,2-diamino-4,5-dimethoxybenzene, 4,4'-diamino-2,2'-stilbenedisulfonic acid, 6,9-diamino-2-ethoxyacridine-DL-lactate monohydrate, 2,2'-diamino-4,4'-stilbenedicarboxylic acid, 3,8-diamino-6-phenylphenanthridine, 2,6-diamino-4-phenyl-1,3,5-triazine, m-xylylenediamine, p-xylylenediamine, o-xylylenediamine, 2,4,6-trimethyl-m-phenanthridine ... phenylenediamine, 2,2,4(2,4,4)-trimethyl-1,6-hexanediamine, 4,4'-methylene-bis(2-methylaniline), 4,4'-methylene-bis(2-chloroaniline), 2,5-dichloro-p-phenylenediamine, 4,4'-dibromo-2,2'-biphenyldiamine, 2,6-diaminotoluene, 2-methyl-m-phenylenediamine, benzidine, 2,4-diaminobenzenesulfonic acid, 2,4-diaminophenol dihydrochloride, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,2-diaminoanthraquinone, 3,5-diaminobenzoic acid dihydrochloride, and 4,4'-diaminobenzanilide.

[0012] In certain embodiments, the binding compound containing two or more amine groups includes, but is not limited to, 3,5-diamino-1,2,4-triazole, 2,4-diamino-6-hydroxypyrimidine, 5,6-diamino-1,3-dimethyluracil hydrate, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-(hydroxymethyl)pteridine, 2,4-diamino-6-(hydroxymethyl)pteridine hydrochloride, 2,6-diamino-3,5-difluoropyridine, 2-chloro- 4,6-diamino-1,3,5-triazine, 2-nitro-1,4-phenylenediamine, 2,6-diaminopurine-9-arabinoside, melamine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyrimidine, lysine, esters of lysine such as lysine methyl ester and lysine ethyl ester, arginine, esters of arginine such as arginine methyl ester, and histidine. In some embodiments, a linking compound having two or more thiol groups can be reacted with one or more UV-absorbing compounds having alkene groups to form a UV-absorbing linking compound containing a thioether. Alkene groups include, but are not limited to, vinyl, acrylate, methacrylate, cyanoacrylate, or acrylamide groups. Linking compounds that are alkanes having two or more thiol groups include, but are not limited to, C2 to C20 dithiols, dithiothreitol, 2,3-dimercapto-1-propanol, and 2,3-dimercaptosuccinic acid.

[0013] In certain embodiments, binding compounds comprising a benzene ring and at least two thiol groups include, but are not limited to, 1,4-benzenedimethanethiol, 1,4-benzenedimethanethiol, benzene-1,2-dithiol, benzene-1,4-dithiol, 1,3-benzenedithiol, biphenyl-4,4′-dithiol, and p-terphenyl-4,4″-dithiol. In certain embodiments, binding compounds comprising at least one thiol and one amine group include, but are not limited to, 2-aminobutane-1,4-dithiol hydrochloride, 4,5-diamino-2,6-dimercaptopyrimidine, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, and 4,6-diamino-2-pyrimidinethiol. In some embodiments, the present disclosure includes a coupling compound containing two or more hydrazides. One or more hydrazide groups can react with the carboxylic acid group of a UV-absorbing compound. Dihydrazide compounds include, but are not limited to, saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms, carbohydrazides, thiocarbohydrazides, adipic acid dihydrazide, succinic acid dihydrazide, oxalyl dihydrazide, ethylmalonic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, pimelic acid dihydrazide, and pyromellitic acid dihydrazide. Trihydrazide-linked compounds include, but are not limited to, 1,2,4-butanetricarboxylic acid trihydrazide, citric acid trihydrazide, 1,3,5-benzene(tricarboxylic trihydrazide), nitriloacetotrihydrazide, 1,2,4-benzenetrihydrazide, and cyanuric acid trihydrazide.Tetrahydrazide-linked compounds include, but are not limited to, ethylenediaminetetraacetic acid tetrahydrazide and 1,4,5,8-naphthoic acid tetrahydrazide.

[0014] The binding compound can comprise a polymer. These terms, referred to herein as "binding polymers," include homopolymers and copolymers. In some embodiments, the binding polymer comprises a non-absorbing polymer. Non-absorbing polymers can include polymers containing one or more amine groups, one or more carboxylic acid groups, one or more thiol groups, one or more hydrazide groups, or a combination thereof. The binding polymers disclosed herein can have two or more repeating units. In some embodiments, the disclosed polymers can have a molecular weight greater than 200 Daltons. In some embodiments, the molecular weight of the binding polymer is greater than about 1,000. In some embodiments, the molecular weight of the binding polymer is greater than about 5,000. Examples of binding polymers include, but are not limited to, polyalkylene oxide polymers containing one or more amine, carboxylic acid, thiol, or hydrazide groups. Examples of polyalkylene oxide binding polymers include, but are not limited to, methoxypolyethylene glycol, polyethylene glycol, polypropylene glycol, or copolymers of ethylene oxide and propylene oxide. In some embodiments, the binding polymer can include one or more amine groups capable of reacting with the carboxylic acid group of the UV-absorbing compound. Binding polymers containing one or more amine groups include, but are not limited to, poly(ethyleneimine), poly(vinylamine) hydrochloride and copolymers thereof, poly(allylamine) and copolymers thereof, poly(4-aminostyrene) and copolymers thereof, poly(N-methylvinylamine) and copolymers thereof, poly(ethylene glycol) bis(2-aminoethyl), poly(2-aminoethylmethacrylamide) and copolymers thereof, poly(N-(3-aminopropyl)methacrylamide) and copolymers thereof, 3-arm PEG amine (glycerol core), 4-arm PEG amine (pentaerythritol core), 6-arm PEG amine (dipentaerythritol core), 8-arm PEG amine (hexaglycerol core), 8-arm PEG amine (tripentaerythritol core), methoxy PEG acetate, methoxy PEG butanoate, methoxy PEG hexanoate, methoxy PEG propionic acid, PEG(acetate) 2,4-arm PEG acetate, 6-arm PEG acetate, and 8-arm PEG acetate.

[0015] In some embodiments, the binding polymer can contain one or more hydrazide groups capable of reacting with the carboxylic acid groups of the UV-absorbing compound to form a UV-absorbing binding compound having a -CO-NH-NH-CO- bond. Examples of binding polymers containing one or more hydrazide groups include, but are not limited to, methoxy PEG hydrazide, PEG dihydrazide, 3-arm PEG hydrazide, 4-arm PEG hydrazide, 6-arm PEG hydrazide, 8-arm PEG hydrazide, and poly(acryloyl hydrazide). The binding polymer containing one or more hydrazide groups can be prepared from a polymer containing a carboxylic acid group, an acrylonitrile group, or an acrylamide group. Examples of these polymers are described in U.S. Patent Application Publication No. 20070225453, which is incorporated herein by reference. Polyhydrazides can be obtained by reacting a polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (see Japanese Patent Publication No. 52-22878). Polyhydrazides can be obtained by reacting a polycarboxylic acid-containing polymer with an excess of a dihydrazide compound such that the resulting polymer has residual hydrazide groups that can react with the carboxylic acid moieties of a UV-absorbing compound.

[0016] In some embodiments, the binding polymer can contain one or more thiol groups that can react with the acrylate, methacrylate, acrylamide, or alkene groups of the UV-absorbing compound to form a UV-absorbing binding compound having a thioether bond. Polymers containing one or more thiol groups include, but are not limited to, methoxy PEG thiol, PEG dithiol, 3-arm PEG thiol, 4-arm PEG thiol, and 8-arm PEG thiol. In some embodiments, the binding polymer can contain one or more carboxylic acid groups that can react with the amine or hydrazide groups of the UV-absorbing compound to form a UV-absorbing binding compound having an amide or -CO-NHNH-CO- linkage, respectively. In some embodiments, non-degradable polymers containing one or more carboxylic acid groups include, but are not limited to, poly(acrylic acid) and its copolymers, poly(malic acid) and its copolymers, poly(maleic acid) and its copolymers, poly(fumaric acid) and its copolymers, poly(2-carboxyethyl acrylate) and its copolymers, poly(4-vinylbenzoic acid) and its copolymers, poly(maleic acid, mono-2-acryloxyethyl ester) and its copolymers, poly(methacrylic acid) and its copolymers, and poly(phthalic acid, mono-2-acryloxyethyl ester) and its copolymers.

[0017] The UV-absorbing polymeric compound can be prepared by free-radical polymerization of a monomer composition containing at least one UV-absorbing compound capable of free-radical polymerization, resulting in the UV-absorbing polymeric compound of formula 2 and / or 4. Examples of UV-absorbing compounds capable of free-radical polymerization include, but are not limited to, UV-absorbing compounds containing vinyl, acrylate, methacrylate, or acrylamide groups. Examples of UV-absorbing compounds include, but are not limited to, N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide (CAS 107479-06-1) and 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (CAS 96478-09-0). In some embodiments, the free-radical polymerizable monomer includes, but is not limited to, a monomer containing a vinyl, acrylate, methacrylate, or acrylamide group. The monomer can include a hydrophilic or hydrophobic monomer. Monomers that can be used include, but are not limited to, those supplied by Polysciences, Inc., which are incorporated herein by reference. The ratio of monomer to initiator can be adjusted to alter the molecular weight of the resulting polymer.

[0018] The monomer compositions disclosed herein can further include a cross-linking agent to produce a cross-linked solid composition. The cross-linked composition can be further processed, such as by grinding, pulverizing, sieving, or a combination thereof, to produce microparticles or nanoparticles. In some embodiments, emulsion polymerization can be used to prepare the cross-linked particles; such polymerization reactions are known to those skilled in the art. In some embodiments, the conjugated polymeric compounds are degradable. In some embodiments, the conjugated polymeric compounds are hydrolytically stable at pH 6.5 to pH 7.5 for at least six months. In some embodiments, the conjugated polymeric compounds are enzymatically cleavable. In some embodiments, the conjugated polymeric compounds are hydrolytically stable at pH 6.5 to pH 7.5 for at least six months, but are cleaved upon exposure to an appropriate enzyme. In some embodiments, the enzymatically degradable conjugated polymer compound comprises a protein, peptide, or polypeptide. In some embodiments, the protein, peptide, or polypeptide has one or more available amino groups that react with at least one UV-absorbing compound. Such compounds include, but are not limited to, proteins, peptides, or polypeptides that have one or more lysine moieties. Compounds that contain one or more lysine moieties include, but are not limited to, poly(lysine). In some embodiments, the protein, peptide, or polypeptide has one or more available thiol groups that react with a UV-absorbing compound. Such conjugated polymeric compounds include, but are not limited to, proteins, peptides, or polypeptides that have one or more cysteine ​​moieties. Conjugated polymeric compounds that contain one or more cysteines include, but are not limited to, poly(cysteine). In some embodiments, the protein, peptide, or polypeptide has one or more available carboxylic acid groups that react with a UV-absorbing compound. Such conjugated polymeric compounds include, but are not limited to, proteins, peptides, or polypeptides having one or more carboxylic acid moieties. Conjugated polymeric compounds containing one or more carboxylic acids include, but are not limited to, poly(aspartic acid) and its copolymers, poly(glutamic acid) and its copolymers. In some embodiments, the protein, peptide, or polypeptide-bound polymeric compound has one or more available amine and thiol groups that react with a UV-absorbing compound.

[0019] In some embodiments, the binding polymer compound may comprise a polysaccharide. Polysaccharides that are enzymatically degradable and have one or more functional groups that can react with functional groups on a UV-absorbing compound or a derivative of a UV-absorbing compound can be used to prepare the UV-absorbing binding compound. Types of polysaccharides that can be used in the disclosed compositions include, but are not limited to, hyaluronic acid, alginic acid, cellulose, dextran, chitin, chitosan, xanthan gum, xylan, guar gum, pullulan, locust bean gum, starch, glucogen, cyclodextrin, amarose, amylopectin, pectin, callose, laminarin, chrysolaminarin, arabinoxylan, mannan, fucoidan, and galactomannan. These types include derivatives and salts thereof. For example, cellulose derivatives include, but are not limited to, cellulose esters, cellulose ethers, and nitrocellulose. Cellulose esters include, but are not limited to, cellulose acetate, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB). Cellulose ethers include, but are not limited to, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, methylethylhydroxyethylcellulose, and ethylhydroxyethylcellulose. Salts of alginic acid include, but are not limited to, sodium alginate and calcium alginate. In order for the polysaccharide or its derivative to react with a UV-absorbing compound, the polysaccharide contains at least one functional group capable of reacting with a functional group of the UV-absorbing compound. Functional groups that can be used to react with the UV-absorbing compound include, but are not limited to, hydroxyl, carboxylic acid, thiol, amine, acrylate, methacrylate, vinyl, acrylamide, hydrazide, allyl, and vinyl sulfone groups.

[0020] In some embodiments, the polysaccharide contains amine groups. The amine groups of the polysaccharide can react with the carboxylic acid groups of the UV-absorbing compound to form amine groups. The amine groups of the polysaccharide can react with the acrylate, acrylamide, or methacrylate groups of the UV-absorbing compound via a Michael addition reaction. In some embodiments, amine-containing polysaccharides include, but are not limited to, aminodextran, aminocyclodextrin, chitosan, aminocellulose, and deacetylated hyaluronic acid. The aminodextran used can have a molecular weight of more than 1000 Daltons. Aminocyclodextrin compounds include, but are not limited to, 6-monodeoxy-6-monoamino-β-cyclodextrin hydrochloride (CAS 29390-67-8), heptakis-(6-amino-6-deoxy)-beta-cyclodextrin heptahydrochloride (CAS 65024-90-0), heptakis-(2,3-di-O-methyl-6-amino-6-deoxy)-β-cyclodextrin heptahydrochloride, 6-monoamino-6-monodeoxy-permethyl-β-cyclodextrin hydrochloride, A,D-6-diamino-6-dideoxy-β-cyclodextrin dihydrochloride, hexakis-(2,3-di-O-methyl-6- Examples of suitable cyclodextrins include A,D-6-diamino-6-dideoxy-α-cyclodextrin dihydrochloride, hexakis-(6-amino-6-deoxy)-α-cyclodextrin hexahydrochloride, A,D-6-diamino-6-dideoxy-α-cyclodextrin dihydrochloride, hexakis-(6-amino-6-deoxy)-α-cyclodextrin hexahydrochloride, octakis-(6-amino-6-deoxy)-γ-cyclodextrin octahydrochloride, octakis-(2,3-di-O-methyl-6-amino-6-deoxy)-γ-cyclodextrin octahydrochloride, 6-monoamino-6-monodeoxy-γ-cyclodextrin hydrochloride, and 6alpha-[(2-aminoethyl)amino]-6a-deoxy-betacyclodextrin. Aminocelluloses include, but are not limited to, 6-deoxy-6-(ω-aminoalkyl)aminocellulose carbamates. Amino-containing hyaluronic acid derivatives include, but are not limited to, deacetylated hyaluronic acid.

[0021] In some embodiments, the polysaccharide contains thiol groups. The thiol groups of the polysaccharide can react with the acrylate, acrylamide, or methacrylate groups of the UV-absorbing compound via a Michael addition reaction to form a thioether. Examples of thiolated cyclodextrins include, but are not limited to, heptakis-(6-deoxy-6-mercapto)-beta-cyclodextrin (CAS 160661-60-9), hexakis-(6-deoxy-6-mercapto)-α-cyclodextrin, and octakis-(6-deoxy-6-mercapto)-γ-cyclodextrin. Thiolated chitosans can include, but are not limited to, alkylthiolated chitosan derivatives such as chitosan-cysteine, chitosan-thiobutylamidine, chitosan-thioglycolic acid, chitosan-N-acetylcysteine, and chitosan-thioethylamidine, and arylthiolated chitosans such as chitosan-6-mercaptonicotinic acid and chitosan-4-mercaptobenzoic acid. The preparation of thiolated chitosan derivatives is described in detail in International Publication No. 2015169728, Kast, Constantia E; Frick, Wolfram; Losert, Udo; Bernkop-Schnurch, Andreas, International Journal of Pharmaceutics, Volume 256(1)-Apr 30, 2003, Roldo, Marta & Hornof, Margit & Caliceti, Paolo & Bernkop-Schnurch, Andreas. (2004), which is incorporated herein by reference. Thiolated hyaluronic acid can be prepared according to U.S. Patent Application Publication Nos. 20100330143 and 20080031854. U.S. Patent Application Publication Nos. 20100144902 and 20100152423 are incorporated herein by reference.

[0022] In some embodiments, the polysaccharide can contain one or more hydrazide groups. In some embodiments, the hydrazide-containing polysaccharide is derived from a polysaccharide containing one or more carboxylic acid groups, and the one or more carboxylic acid groups are reacted with a dihydrazide compound to result in a derivatized polysaccharide containing one or more hydrazide groups. In some embodiments, the polysaccharide containing one or more carboxylic acid groups includes, but is not limited to, hyaluronic acid, galacturonan, xylogalacturonan, apiogalacturonan, alginic acid, carboxymethylcellulose, and cellulose acetate phthalate. In some embodiments, the hydrazide polysaccharide can include, but is not limited to, hydrazide-derivatized hyaluronic acid, hydrazide-derivatized carboxymethylcellulose, hydrazide-derivatized cellulose acetate phthalate, hydrazide-derivatized alginic acid, and hydrazide-derivatized galacturonan. Hydrazide-functionalized hyaluronic acid can be prepared according to US Patent Application Publication Nos. 20100330143, 20100144902, and 20100152423, which are incorporated herein by reference. In some embodiments, polysaccharides can be enzymatically degraded: hyaluronic acid can be degraded by hyaluronidase, chitosan can be degraded by lysozyme, cellulosic polymers and oligomers can be degraded by cellulases and endoglucanases, and dextran can be degraded by dextranase.

[0023] In some embodiments, the conjugated polymer compound may comprise a polyamino acid. The polyamino acid may comprise a peptide and / or a protein. A peptide is a compound having two or more amino acids. A UV-absorbing compound having a carboxylic acid group or a sulfonic acid group can react with the terminal amine group of the peptide or protein to form an amide or sulfonamide bond, respectively, between the UV-absorbing compound and the peptide or protein. UV-absorbing binding compounds having two or more UV-absorbing compounds bound thereto can be prepared using proteins or peptides containing one or more amine-containing amino acids. Suitable amine-containing amino acids include lysine, arginine, and histidine. UV-absorbing compounds having carboxylic or sulfonic acid groups can react with the terminal amine groups and amine groups of the amine-containing amino acids of peptides or proteins, forming amide or sulfonamide bonds, respectively, between the UV-absorbing compounds and the peptides or proteins. A UV-absorbing compound having a hydrazide group can react with the terminal carboxylic acid group of a peptide or protein, forming a bond between the UV-absorbing compound and the peptide or protein. A UV-absorbing compound having a hydrazide group can react with the terminal carboxylic acid group of a peptide or protein and any carboxylic acid-containing amino acid within the peptide or protein, forming a bond between the UV-absorbing compound and the peptide or protein. Suitable carboxylic acid-containing amino acids include one or more of aspartic acid and glutamic acid. In some embodiments, the peptide is poly(glutamic acid), poly(aspartic acid), or a combination thereof. In some embodiments, the binding compound can be hydrolyzed collagen. In some embodiments, the hydrolyzed collagen can be gelatin containing glutamic acid. UV-absorbing binding compounds having two or more UV-absorbing compounds bound thereto can be prepared using proteins or peptides containing one or more amine-containing amino acids. Suitable amine-containing amino acids include lysine, arginine, and histidine. In some embodiments, the peptide is poly(lysine), polyarginine, or poly(histidine), or a combination thereof. In some embodiments, the binding compound can be hydrolyzed collagen. In some embodiments, the hydrolyzed collagen can be gelatin containing arginine.

[0024] UV-absorbing compounds having an alkene group can react with peptides or proteins that contain one or more free thiol groups. In some embodiments, the peptide or protein contains one or more cysteine ​​groups, but the thiols are free and not part of a disulfide bond. The UV-absorbing binding compound, including polysaccharides or polyamino acids, can be crosslinked. Suitable crosslinkers include, but are not limited to, compounds containing two or more vinyl sulfone groups, epoxide groups, isocyanate groups, or carbodiimide groups. The crosslinked material can be further processed, such as by grinding, pulverizing, sieving, or a combination thereof, to produce microparticles or nanoparticles. In some embodiments, the crosslinking reaction can be carried out as an emulsion to produce crosslinked particles.

[0025] In another embodiment, the polysaccharide- or polyamino acid-binding compound can be made into crosslinked particles by an emulsification reaction or through a crosslinking reaction, followed by further processing such as grinding, pulverizing, sieving, or a combination thereof. The polysaccharide or polyamino acid can be crosslinked using a suitable crosslinking agent. In some embodiments, the crosslinking reaction can be an emulsion reaction, resulting in the formation of particles. In some embodiments, the crosslinked material can be converted into a particulate form by a process including grinding, pulverizing, sieving, or a combination thereof. As described herein, the crosslinked particles can be reacted with a UV-absorbing compound such that the UV-absorbing compound chemically bonds to the pre-crosslinked particles. Prior to the cross-linking reaction, the UV-absorbing binding compound can be incorporated into a polysaccharide or polyamino acid, and then entrapped in the cross-linked material. In some embodiments, the cross-linking reaction can be an emulsion reaction, resulting in the formation of particles. In some embodiments, the cross-linked material can be converted into a particulate form by a process including grinding, pulverizing, sieving, or a combination thereof. A UV-absorbing compound containing a hydrazide group can react with residual carboxylic acid groups of a degradable polyester using a carbodiimide to activate the ester. In some embodiments, an initiator containing both at least one hydroxyl group and at least one carboxylic acid group can be used to initiate the ring-opening polymerization of the polyester. Monomers that can be used include glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, and morpholinedione. Initiators that can be used include, but are not limited to, hydroxyalkanecarboxylic acid compounds. Examples of hydroxyalkanecarboxylic acid compounds include, but are not limited to, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 11-hydroxyundecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxyoctadecanoic acid, 12-hydroxystearic acid, citric acid, glycolic acid, and tartaric acid. The molecular weight of the polyester is greater than 1,000 daltons. In some embodiments, the molecular weight is greater than 1500.

[0026] UV absorbing compounds UV-absorbing compounds absorb UV radiation having wavelengths less than 400 nm, e.g., between 200 and 400 nm. UV-absorbing compounds can absorb, for example, UV-A (320 to 400 nm), UV-B (290 to 319 nm), and / or UV-C (200 to 289 nm) light. In some embodiments, UV-absorbing compounds absorb UV-A and / or UV-B radiation. In some embodiments, UV-absorbing compounds absorb UV-A and / or UV-B radiation and non-radiatively inactivate the absorbed radiation energy. Examples of UV-absorbing compounds include, but are not limited to, benzophenone-based compounds, benzotriazole-based compounds, and benzimidazole-based compounds with absorbance in the 200 to 400 nm range. In some embodiments, UV-absorbing compounds include, but are not limited to, benzophenone-based compounds, benzotriazole-based compounds, and benzimidazole-based compounds with absorbance in the 200 to 380 nm range. In certain embodiments, UV absorbing compounds include, but are not limited to, benzophenone-based compounds, benzotriazole-based compounds, and benzimidazole-based compounds having absorbance in the range of 200 to 350 nm. Disclosed herein are UV-absorbing compounds having acrylamide, acrylate, methacrylate, maleimide, acrylonitrile, vinyl sulfone, amine, sulfonic acid, allyl, hydrazide, and / or carboxylic acid groups available for reaction with a linking compound. In some embodiments, UV-absorbing compounds containing acrylamide, acrylate, methacrylate, maleimide, acrylonitrile, or vinyl sulfone groups capable of Michael addition can be used to prepare the linking compound. UV-absorbing compounds containing one or more functional groups capable of Michael addition can be linked to compounds having one or more amine groups, thiol groups, or combinations thereof. UV-absorbing compounds that can be used include, but are not limited to, UV-absorbing benzotriazole compounds having acrylamide, acrylate, methacrylate, maleimide, acrylonitrile, or vinyl sulfone groups. Examples of these compounds include, but are not limited to, N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide (CAS 107479-06-1) and 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (CAS 96478-09-0).

[0027] In some embodiments, the present disclosure provides UV-absorbing compounds that contain a carboxylic acid group that can react with the amine group of a compound to be linked to form an amide bond. The UV-absorbing compounds include benzotriazole compounds that contain a carboxylic acid group. Benzotriazole compounds that contain a carboxylic acid group include, but are not limited to, 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0). The UV-absorbing compound can contain a hydrazide group. The hydrazide-containing UV-absorbing compound can react with a linking compound containing one or more carboxylic acid groups. In one embodiment, the hydrazide UV-absorbing compound is prepared by reacting 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid with an excess of dihydrazide. The reaction product contains a hydrazide group chemically bonded to the UV-absorbing compound.

[0028] In some embodiments, the UV-absorbing compound contains an alkene group capable of undergoing a thiol-ene reaction with the thiol group of the binding compound. Examples of alkene-containing UV-absorbing compounds include, but are not limited to, benzotriazole compounds containing an alkene group. Examples of benzotriazole compounds containing an alkene group include, but are not limited to, N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide (CAS 107479-06-1), 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (CAS 96478-09-0), and 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (CAS 2170-39-0). In some embodiments, the thiol-ene reaction can occur in the presence of a photoinitiator and a light source. In some embodiments, the light source emits ultraviolet light. Thiol-ene reactions can be initiated by cleavage-type photoinitiators, also known as Norrish Type I photoinitiators, and H-abstraction-type photoinitiators, also known as Norrish Type II photoinitiators. Cleavage-type photoinitiators include, but are not limited to, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxy-cyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TMDPO), and 2,2-dimethoxy-2-phenylacetophenone (DMPA). H-abstraction-type photoinitiators include, but are not limited to, benzophenone (B), thioxanthone (TX), isopropylthioxanthone, and camphorquinone (CQ). Photoinitiators also include the Irgacure series of photoinitiators from BASF / Ciba. The thiol-ene reaction can be initiated by thermal initiators, including but not limited to 2,2'-azobis(isobutyronitrile) (AIBN) and benzoyl peroxide.

[0029] In some embodiments, UV-absorbing compounds containing sulfonic acid groups can react with the amine groups of the compound to be linked, forming sulfonamide bonds. Examples of sulfonic acid-containing UV-absorbing compounds include, but are not limited to, sulfonic acid group-containing benzimidazole compounds, sulfonic acid group-containing benzotriazole compounds, and sulfonic acid group-containing benzophenone compounds. Examples of sulfonic acid group-containing benzimidazole compounds include, but are not limited to, 2-phenylbenzimidazole-5-sulfonic acid, or ensulizole (CAS 27503-81-7). Examples of sulfonic acid group-containing benzophenone compounds include, but are not limited to, sulisobenzone, or benzophenone-4 (CAS 4065-45-6). Examples of benzotriazole compounds containing sulfonic acid groups include, but are not limited to, sodium 3-(benzotriazol-2-yl)-5-butan-2-yl-4-hydroxybenzenesulfonate (CAS 92484-48-5), 3-(benzotriazol-2-yl)-5-butan-2-yl-4-hydroxybenzenesulfonic acid, 2-(2-hydroxy-3,5-dimethylphenyl)benzotriazole-4-sulfonic acid, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole-5-sulfonic acid, 2-(5-tert-butyl-2-hydroxy-3-propan-2-ylphenyl)benzotriazole-5-sulfonic acid, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonic acid, and 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxybenzenesulfonic acid.

[0030] The disclosed UV-absorbing binding compounds may be formed into or incorporated into particles, spheres, hollow spheres, fibers, hollow fibers, or liposomes. The disclosed UV-absorbing binding compounds may be incorporated into particles, spheres, hollow spheres, fibers, or hollow fibers formed from a matrix material. In some embodiments, the matrix material may be a polymer, glass, or inorganic matrix. The disclosed UV-absorbing binding compounds may be coated onto particles, spheres, hollow spheres, fibers, or hollow fibers formed from a matrix material. The disclosed UV-absorbing binding compounds may be incorporated into the cavities of hollow spheres, hollow fibers, or porous inorganic matrices. In some embodiments, the average diameter of the particles, spheres, hollow spheres, or liposomes is less than about 500 nm. In some embodiments, the average diameter of the particles, spheres, hollow spheres, or liposomes is less than about 400 nm. In some embodiments, the average diameter of the particles, spheres, hollow spheres, or liposomes is less than about 300 nm. The UV-absorbing binding compounds disclosed herein can be incorporated into formulations that can be applied to one or more body surfaces, such as sunscreens, cosmetics, or hair products. Sunscreen compositions can include, but are not limited to, everyday sunscreens, water-resistant sunscreens, or combinations thereof. Cosmetic compositions can include, but are not limited to, formulations such as moisturizers, foundations, lipsticks, lip glosses, chapsticks, concealers, highlighters, blushes, eye shadows, makeup removers, toners, serums, anti-aging products, fixative sprays, or combinations thereof. Hair product compositions can include, but are not limited to, shampoos, conditioners, leave-in conditioners, hair mousses, hair gels, hair sprays, curl creams, hair waxes, treatment oils, medicated hair treatments, or combinations thereof.

[0031] The formulations containing the disclosed UV-absorbing binding compounds can be prepared by methods well known to those skilled in the art of cosmetic formulation. Formulations of various formulations are known. These forms include, but are not limited to, solutions, suspensions, emulsions, liposomes, dispersions, and microparticles. Product forms of sunscreen, makeup, or hair formulations include, but are not limited to, liquids, sprays, gels, lotions, creams, mousses, emulsions, sticks, powders, or combinations thereof. In some embodiments, the formulation compositions disclosed herein, such as sunscreen, cosmetic, or hair formulations, may be emulsions. In some embodiments, the formulation is an oil-in-water (o / w) emulsion having a continuous aqueous phase and a discontinuous oil phase. Moisturizers or sunscreen lotions are examples of oil-in-water compositions. In some embodiments, the formulation is a water-in-oil (w / o) emulsion having a continuous oil phase and a discontinuous aqueous phase. Sunscreen cream formulation compositions may be water-in-oil compositions. In some embodiments, the UV-absorbing binding compound can be present in the aqueous phase. In some embodiments, the UV-absorbing binding compound can be present in the oil phase. In some embodiments, the UV-absorbing binding compound can be present in both the aqueous and oil phases. In some embodiments, the formulation composition may contain two or more different UV-absorbing binding compounds, where one UV-absorbing binding compound is present in the aqueous phase and another is present in the oil phase. In some embodiments, the formulation contains two or more different UV-absorbing binding compounds, optionally where one UV-absorbing binding compound is present in the aqueous phase and another is present in the oil phase and / or aqueous phase. In some embodiments, the formulation comprises two or more different UV-absorbing binding compounds, one UV-absorbing binding compound being present in the oil phase and the other being present in the oil and / or water phases. For example, the water content of an oil-in-water emulsion can be about 40% (w / w) to 80% (w / w) of the final formulation, hi some embodiments, the water content can be about 50% (w / w) to about 70% (w / w) of the final formulation.

[0032] Emulsifier The formulation compositions disclosed herein include one or more UV-absorbing binding compounds and may include an emulsifier. Water-in-oil emulsifiers include, but are not limited to, glyceryl stearate, lecithin, polyglyceryl oleate, sorbitan stearate, glycol stearate, glyceryl oleate, sorbitan oleate, laureth-3, PEG-8 beeswax, glycol distearate, shea butter glycerides, methyl glucose dioleate, hydroxylanolin, and emulsifiers sold by Evonik. See personal-care.evonik.com / product / personal-care / en / products-solutions / products / pages / default.aspx?category=3591. Oil-in-water emulsifiers include, but are not limited to, ceteareth-20, ceteareth-25, gum arabic, PEG-7 glyceryl cocoate, PEG-40 hydrogenated castor oil, polysorbate 20, polysorbate 60, polysorbate 80, PEG-150 distearate, cetearyl alcohol, stearic acid, glyceryl stearate citrate, laneth-16, ceteth-16, oleth-16, steareth-16, stearyl alcohol, emulsifiers available from Evonik. See personal-care.evonik.com / product / personal-care / en / products-solutions / products / pages / default.aspx?category=3496.

[0033] Formulation compositions containing one or more UV absorbing binding compounds may include an emollient, including, but not limited to, petrolatum, silicone oil, castor oil, lanolin, cocoa butter, liquid paraffin, cetyl alcohol, cetearyl alcohol, isopropyl myristate, isopropyl palmitate, shea butter, stearic acid, steryl alcohol, vegetable oils, and combinations thereof. Formulation compositions containing one or more UV absorbing binding compounds may include a humectant, including, but not limited to, algae extract, aloe vera, aloe vera palmitate, butylene glycol, caprylyl glycol, ethoxydiglycol, glycerin, hexanediol, honey, hyaluronic acid, methyl gluceth-10, pentylene glycol, propanediol, propylene glycol, sorbitol, sucrose cocoate, urea, sodium lactate, and combinations thereof. The formulation composition comprising one or more UV absorbing binding compounds may also comprise a conditioning agent, including but not limited to cocamidopropyl betaine, stearamidopropyl dimethylamine, trioctyldodecyl citrate, PEG / PPG-8 / 3 diisostearate, myristamidopropyl dimethylamine phosphate (and) propylene glycol, polyquaternium-6, polyquaternium-47, polyquaternium-53, polyquaternium-7, polyquaternium-10, polyquaternium-22, polyquaternium-39, polyquaternium-5, acetylated lanolin, cetearyl alcohol (and) cetrimonium bromide, soyamidopropalkonium chloride. PEG-14 Dimethicone, Cocamidopropyl Betaine, Cocamidopropyl Dimethylamine, Isostearamidopropyl Dimethylamine, Acetamide MEA, Isostearamidopropyl Lauryl Acetodimonium Chloride (and) Propylene Glycol, Isostearamidopropyl Ethyldimonium Ethosulfate (and) Propylene Glycol, Hydroxypropyltrimonium Starch Chloride, PEG-7 Amodimethicone, PEG-33 (and) PEG-8 Dimethicone (and) PEG-14, Dimethiconol Stearate, PEG-8 Dimethicone Phosphate, Silicone Quaternium-8, PEG-7 Dimethicone Cocoate, Dimethicone PEG-8 Beeswax, and combinations thereof. Formulation compositions containing one or more UV absorbing binding compounds may include inorganic particulates, including but not limited to glass particles, glass beads, dyes, zinc oxide, and titanium dioxide.

[0034] The formulation composition containing one or more UV-absorbing binding compounds may also contain a compound that enhances the water resistance of the formulation. Compounds that enhance the water resistance of the formulation include, but are not limited to, film-forming polymers. Polymers that can be used include, but are not limited to, dehydroxanthan gum, Dermacryl AQF polymer, bisPEG-18 methyl ether dimethyl silane, trimethylsiloxysilicate, and butylated PVP (polyvinylpyrrolidone), octylacrylamide / acrylates copolymer, and octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer. Suitable film-forming polymers for use in the present invention include Amphomer and Amphomer LV-71 polymer (octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer) from National Starch and Chemical Company. butylaminoethyl methacrylate copolymer), Amphomer HC polymer (acrylates / octylacrylamide copolymer), Balance 0 / 55 and Balance CR polymer (acrylates copolymer), Balance 47 polymer (octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer), RESYN 28-2930 polymer (VA / crotonic acid / vinyl neodecanoate copolymer), RESYN 28-1310 polymer (VA / crotonic acid copolymer), DynamX polymer (polyurethane-14 (and) AMP-acrylates copolymer), RESYNXP Polymer (Acrylates / Octyl Acrylamide Copolymer), Structure 2001 (Acrylates / Steareth-20 Itaconate Copolymer), Structure 3001 (Acrylates / Ceteth-20 Itaconate Copolymer), Yodozole 32A707, Yodozole GH15, Yodozole GH32, Yodozole GH33, Yodozole GH34, Yodozole GH35, Yodozole GH256, Yodozole GH800, Yodozole GH810, Yodozole GH 32A707F, Yodozole GH15F, Yodozole GH34F, Yodozole GH800F, Yodozole GH810F, Yodozole GH800PF (Acrylates Copolymer), Yodozole GH52, Yodozole GH52-OP (Styrene / Methacrylamide / Acrylates Copolymer), Yodozole GH265 (Polyacrylate-2), Yodozole GH840, Yodozole GH41F, Yodozole GH41 (Styrene / Acrylates Copolymer), Yodozole PU D (Polyurethane-10 (and) PEG-12 Dimethicone (and) Alcohol), DERMACYL AQF (Acrylates Copolymer), DERMACYL C (Proposed: Acrylates Copolymer) and DERMACYL 79 and LT Polymer (Acrylates / Octyacrylamide Copolymer); ISP's OMNIREZ-2000 (PVM / MA Half Ethyl Ester Copolymer), GANTREDZ A -425 (butyl ester of PVM / MA copolymer), GANTREDZ AN-119 PVM / MA copolymer, GANTREDZ ES225 (ethyl ester of PVM / MA copolymer), GANTREDZ ES-425 (butyl ester of PVM / MA copolymer), AQUAFLEX XL-30 (Polyimide-1), Allianz LT-120 (Acrylates / C1-2 Succinates / Hydroxyalkyl Acrylates Copolymer)Copolymer), Allianz OPT (Acrylates / C12-22 Alkyl Methacrylate Copolymer), Stylese CC-10 (PVP / DMAPA Acrylates Copolymer), Stylese 2000 (VP / Acrylates / Lauryl Methacrylate Copolymer), Stylese W-20 (Polyquaternium-55), Advantage Plus (VA / Butyl Maleate / Isobornyl Acrylate Copolymer); BASF Ultrahold Strong (acrylic acid / ethyl acrylate / t-butyl acrylamide) acrylamide), Rubimer 100P (t-butyl acrylate / ethyl acrylate / methacrylic acid), Rubimer 36D (ethyl acrylate / t-butyl acrylate / methacrylic acid), Rubisset PUR (polyurethane-1), Rubisset Clear (VP / methacrylamide / vinylimidazole copolymer), Rubiflex Soft (acrylate copolymer), Ultrahold 8 (acrylate copolymer), Rubiflex Silk (PEG / PPG-25 / 25 dimethicone / acrylate copolymer) Copolymer), Rubisset CAN (VA / crotonic acid / neodecanoic acid vinyl copolymer), Rubimer PRO55 (acrylate copolymer); Amacol's Amahold DR-25 (acrylic acid / methacrylic acid / acrylates / methacrylates); Rohm and Haas' Accudyne 258 (acrylic acid / methacrylic acid / acrylates / methacrylates / hydroxyalkyl acrylates), Accudyne DHR (acrylates / hydroxyalkyl acrylate copolymer (acrylates / hydroxyesters acrylates)Allianz OPT (Acrylates / C12-22 Alkyl Methacrylate Copolymer); Mitsubishi's Diaformer Z-301, Diaformer Z-SM, and Diaformer Z-400 (Methacryloylethyl Betaine / Acrylates Copolymer), Accudyne 180 (Acrylates / Acrylic Acid Hydroxyester Copolymer), Accudyne SCP (Ethylene Carboxamide / AMPSA / Methacrylates Copolymer), and Accurin Rheology Modifier, distributed by Clariant; Ondeonalco's Fixomer 40 (Acrylates Copolymer), Fixomer A-30, and Fixomer N-28 (INCI Name: Methacrylic Acid / Sodium Acrylamidomethyl Propanesulfonate Copolymer); Eastman Chemical's Eastman Polymer AQ38S and AQ55S (Diglycol / CHDM / Isophthalates / SIP Copolymer) copolymer); vinylpyrrolidone / tricontanyl copolymer, an interpolymer available as Ganex WP660 from ISP; Syntran 5009 and Syntran 5760 (styrene / acrylates / ammonium methacrylate copolymer); Syntran 5190 (acrylates copolymer); Syntran 5900 and 5902 (polystyrene); Syntran 5903, 5904, 5905 (styrene / acrylates copolymer); Syntran KL-219C (ammonium acrylates copolymer); Syntran PC5112 (polyacrylate-16); Syntran PC5208 (polyacrylate-15); Syntran PC5100 (Polyacrylate-21 and Acrylates / Dimethylaminoethyl Methacrylate Copolymer), Syntran PC5107 and PC5117 (Polyacrylate-18 and Polyacrylate-19), Syntran PC5205 and PC5227 (Polyacrylate-15 and Polyacrylate-17); Noveon Fixate G-100 (Acrylates / Allyl Methacrylate Copolymer AMP), Fixate Plus (Polyacrylate-X), Carbopol Ultrez 10 (Carbomer), Carbopol Ultrez 20 (Acrylates / C10-30 Alkyl Acrylate Copolymer), AVALUREAC series (acrylate copolymers), AVALURE UR series (polyurethane-2, polyurethane-4, PPG-17 / IPDI / DMPA copolymers); copolymers of vinylpyrrolidone and long-chain alpha olefins, such as those commercially available from Innolex Chemicals as LEXOREZ TL8 (trimethylpentanediol / adipic acid copolymer, LEXOREZ TC8 and LEXOREZ TC-1 (INCI name: trimethylpentanediol / adipic acid / isononanoic acid copolymer), LEXOREZ 200 (trimethylpentanediol / adipic acid / glycerin crosspolymer), LEXOREZ 100 (adipic acid / diethylene glycol / glycerin crosspolymer), and Ganex V220 from ISP Specialty Chemicals, Wayne, NJ; LEXFILM SUN (polyester-7 and neopentyl glycol diheptanoate), LEXFILM SPRAY (polyester-10 and propylene glycol dibenzoate); Dow Corning's DOW CORNING FA 4002 ID SILICONE ACRYLATE (isododecane and acrylates / polytrimethylsiloxy methacrylate crosspolymer), DOW CORNING FA4001 ID SILICONE ACRYLATE (cyclopentasiloxane and) acrylates / polytrimethylsiloxy methacrylate copolymer); and any combination of the above, hydrogenated dimer dilinoleyl / dimethyl carbonate copolymer available from Cognis, Inc., Ambler, PA as COSMEDIA DC. The film-forming polymer can include polymers that are not or poorly water soluble, as described in WO 2017048706, incorporated herein by reference. The amount of film-forming polymer present in the composition can be from about 0.1% to about 5%, or from about 0.1% to about 3%, or from about 0.1% to about 2%.

[0035] The formulation compositions disclosed herein may contain one or more UV-absorbing conjugates. In some embodiments, the UV-absorbing conjugate compounds are present in an amount effective to provide an SPF of about 10 or greater. In some embodiments, the amount of one or more UV-absorbing conjugate compounds in the formulation composition may vary from about 2% (w / w) to about 60% (w / w) of the final formulation. In some embodiments, the amount of one or more UV-absorbing conjugate compounds present in the formulation may be from about 6% (w / w) to about 40% (w / w) of the final formulation. In some embodiments, the amount of one or more UV-absorbing conjugate compounds in the formulation may be from about 6% (w / w) to about 25% (w / w) of the final formulation. The formulation compositions disclosed herein, including sunscreen, cosmetic, and hair compositions, can include ingredients including, but not limited to, antioxidants, binders, biological additives, buffers, colorants, thickeners, polymers, astringents, fragrances, humectants, opacifiers, conditioners, exfoliating agents, pH adjusters, preservatives, natural extracts, essential oils, skin sensates, skin soothing agents, skin healing agents, SPF boosters, or combinations thereof. In some embodiments, the SPF booster can be an agent capable of reflecting or refracting UV light. In some embodiments, the SPF booster can be a hollow particle, hollow sphere, hollow fiber, porous particle, porous sphere, or porous fiber. In some embodiments, the SPF booster can include a polymer. In some embodiments, the polymer can be a degradable or non-degradable polymer. In some embodiments, the polymer can be a styrene / acrylate copolymer. The formulated compositions disclosed herein, such as sunscreen, cosmetic, and hair compositions, can have a pH of from about 4.0 to about 8.0, or such as from about 5.5 to about 7.0. The compositions and formulations can be used to ameliorate the effects of UV radiation on bodily surfaces, particularly human and animal skin surfaces, for example, by applying an effective amount of a formulation composition disclosed herein, including a UV-absorbing binding compound composition, to human or animal skin in an amount and frequency that provides at least SPF 15 protection to the skin.

[0036] kit The present disclosure includes kits comprising a formulation composition in a container, the formulation composition comprising the UV-absorbing binding compound composition disclosed herein. The kit may further include instructions for use. Disclosed herein are compositions, methods, and kits comprising one or more UV-absorbing binding compound compositions disclosed herein in a container. The kit may further include instructions for use, optionally disposed on or within the container. Disclosed herein are topical pharmaceutical compositions comprising one or more UV absorbing binding compounds having a UV absorbing compound bound to the binding compound. The UV-absorbing compound is selected from the group consisting of: benzophenone-linked compounds formed by linking a benzophenone compound to a linking compound with a sulfonamide linker and having a molecular weight of at least 800 daltons; benzimidazole-linked compounds formed by linking a benzimidazole compound to a linking compound with a sulfonamide linker and having a molecular weight of at least 800 daltons; benzotriazole-linked compounds formed by linking a benzotriazole compound to a linking compound with an amide linker and having a molecular weight of at least 800 daltons; benzotriazole-linked compounds formed by linking a benzotriazole compound to a linking compound with a Michael addition reaction product and having a molecular weight of at least 800 daltons; benzotriazole-functionalized polymers having a molecular weight of at least 800 daltons, in which the benzotriazole is linked to the polymer as a methacrylate, acrylate, or acrylamide derivative of the benzotriazole compound; and benzotriazole-polysaccharide-linked compounds formed by linking a benzotriazole compound to a polysaccharide and having a molecular weight of at least 800 daltons, wherein the UV-absorbing linked compound is not transported through or absorbed by the skin. The UV-absorbing compound is selected from the group consisting of: 1) (UX) n -C, where U is a UV absorbing compound moiety, X is a thioether, amine, amide, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, and n is an integer, n > 1; or 2) (UX) n -C, wherein U is a UV absorbing compound moiety, X is an ester, C is a linking compound moiety, and n is an integer, n≧1; or 3) the UV absorbing linking compound has the structure: [ka] wherein Y is a UV absorbing compound moiety, X is a thioether, amine, amide, ester, urethane, sulfonamide group, -CO-NH-NH-CO-, D is the residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is the residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is the residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n is an integer and n≧1, m and z are each integers and m≧0, z≧0, and the structure can be a block copolymer or a random copolymer; or 4) the UV absorbing binding compound is (UX) n -C-(X-U1) m wherein U is a UV absorbing compound moiety, U1 is a UV absorbing compound moiety having a chemical structure different from U, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, n and m are each an integer, and n and m are ≧1; 5) the UV absorbing linking compound is [ka] wherein Y is a UV absorbing compound moiety, Y1 is a UV absorbing compound moiety having a chemical structure different from Y, X is a thioether, amine, amide, ester, urethane, sulfonamide group, -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n and p are each integers, n and p are ≧1, m and z are each integers, m≧0, z≧0, and the structure can be a block copolymer or a random copolymer.

[0037] Generally, the UV-absorbing binding compound comprises a UV-absorbing compound having a benzophenone-based compound, a benzotriazole-based compound, or a benzimidazole-based compound with an absorbance in the range of about 200 to 380 nm. The UV-absorbing binding compound may comprise one or more UV-absorbing benzotriazole compounds containing reactive residues of acrylamide groups, acrylate groups, methacrylate groups, maleimide groups, acrylonitrile groups, or vinyl sulfone groups. The topical formulation compositions disclosed herein may include sunscreen formulations including everyday use sunscreens, water-resistant sunscreens, or combinations thereof; cosmetic formulations including moisturizers, foundations, lipsticks, lip glosses, chapsticks, concealers, highlighters, blushes, eye shadows, makeup removers, toners, serums, anti-aging products, fixing sprays, or combinations thereof; hair product compositions including shampoos, conditioners, leave-in conditioners, hair mousses, hair gels, hair sprays, curl creams, hair waxes, treatment oils, medicated hair treatments, or combinations thereof.

[0038] definition As used herein, compounds, including organic compounds, can be named using common names recommended by IUPAC, IUBMB, or CAS. When one or more stereochemical features are present, the Cahn-Ingold-Prelog rules of stereochemistry can be used to assign stereochemical priorities, such as E / Z preference. Once named, one of skill in the art can easily verify the structure of the compound either by systematic reduction of the compound structure using the naming rules or by commercially available software such as CHEMDRAW® (CambridgeSoft, Inc., USA). As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "functional group," "alkyl," or "residue" includes mixtures of two or more such functional groups, alkyls, or residues, etc.

[0039] References in the specification and concluding claims to parts by weight of a particular element or component in a composition indicate the mass relationship between the element or component and the other elements or components in the composition or article that the parts by weight represent. For example, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a mass ratio of 2:5, regardless of whether additional components are included in the compound. Unless specifically stated to the contrary, weight percent (wt %) of a component is based on the total weight of the formulation or composition in which the component is included. As used herein, when a compound is referred to as a monomer or compound, it is understood that this is not to be construed as one molecule or one compound, e.g., two monomers generally refers to two different monomers, not two molecules.

[0040] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. As used herein, the terms "about," "approximately," and "at or about" mean that the amount or value in question may be the exact value specified or a value that will provide an equivalent result or effect as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not exact and need not be exact, but may be approximate and / or larger or smaller, as desired, to reflect tolerances, conversion factors, rounding, measurement error, and other factors known to those skilled in the art to provide equivalent results or effects. In some situations, a value that will provide an equivalent result or effect cannot be reasonably determined. In such cases, when used herein, "about" and "at or about" are generally understood to mean a ±10% variation of the nominal value, unless otherwise indicated or implied. Generally, a quantity, size, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "at or about," whether or not expressly stated. When "about," "approximately," or "at or about" is used before a quantitative value, it is understood that the parameter also includes the specific quantitative value itself, unless otherwise specifically stated. As used herein, the term "subject" can be a vertebrate, such as a mammal, fish, bird, reptile, or amphibian. Thus, the subject of the methods disclosed herein can be a human, non-human primate, horse, pig, rabbit, dog, sheep, goat, cow, cat, guinea pig, or rodent. The term does not denote a particular age or sex. Thus, it is intended to encompass adult and newborn subjects, as well as fetuses, regardless of male or female. In some embodiments, the mammalian subject is a human. The term "patient" includes human and animal subjects. As used herein, "administer" and "administration" refer to any method of providing the disclosed compositions to a subject.

[0041] As used herein, the terms "comprises," "comprising," "includes," "including," "containing," "characterized by," "has," "having," or other variations thereof are intended to be non-exclusive inclusions. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to the process, method, article, or apparatus. The term "comprising" may also include limitations associated with the use of "consisting of" or "essentially consisting of." The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, and the claim does not include materials other than those recited except for impurities normally associated with them. When the phrase "consisting of" appears in a passage in the body of a claim rather than immediately following the preamble, it limits only the elements recited in that passage and does not exclude other elements from the claim as a whole. The transitional phrase "consisting essentially of" limits the scope of a claim to specific materials or steps, and those that do not materially affect the basic and novel characteristics of the claimed invention. A "consisting essentially of" claim is intermediate between a closed claim written in the "consisting of" format and a fully open claim written in the "comprising" format. Reasonable amounts of optional additives, as defined herein, and minor impurities are not excluded from the composition by the term "consisting essentially of." When a composition, process, structure, or portion of a composition, process, or structure is described herein using open-ended terminology such as "comprising," unless otherwise indicated, the description also includes embodiments that "consists essentially of" or "consists of" the composition, process, structure, or portion of the composition, process, or structure.

[0042] The articles "a" and "an" may be used in connection with various elements and components of the compositions, processes, or structures disclosed herein. This is done merely for convenience and to give a general sense of the composition, process, or structure. Such descriptions include "one or at least one" of the element or component. Furthermore, as used herein, singular articles also include descriptions of plural elements or components, unless it is clear from the specific context that a plurality is excluded. The term "about" indicates that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, to reflect tolerances, conversion factors, rounding, measurement error, etc., and other factors known to those of skill in the art. In general, amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate," whether or not expressly stated.

[0043] As used herein, the term "or" is inclusive, i.e., the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist). Exclusive "or" is designated herein by terms such as "either A or B" and "one of A or B." Also, ranges set forth herein include endpoints unless expressly indicated otherwise. Furthermore, when an amount, concentration, or other value or parameter is given as a range, as one or more preferred ranges, or as a list of maximum and minimum preferred values, this is to be understood as specifically disclosing all values ​​formed from any pair of any upper range or preferred value and any lower range or preferred value, regardless of whether such pair is otherwise disclosed. The scope of the present invention is not limited to the specific values ​​recited when defining a range. When a material, method, or machine is described herein using the term "known to those skilled in the art," "conventional," or equivalent words or phrases, this term means that materials, methods, and machines that are conventional at the time of filing of this application are encompassed by the description. Materials, methods, and machines that are not now conventional, but that would be recognized in the art as being suitable for similar purposes, are also encompassed.

[0044] Unless otherwise indicated, all percentages, parts, ratios and similar amounts are defined by weight. All patents, patent applications, and literature citations contained herein are specifically incorporated by reference in their entirety. Of course, it should be understood that the above relates only to preferred embodiments of the present disclosure, and that numerous changes or modifications may be made thereto without departing from the spirit and scope of the present disclosure as set forth herein. Furthermore, the present disclosure is illustrated by examples, which should not be construed in any way as limiting its scope. On the contrary, it should be clearly understood that various other embodiments, modifications and equivalents may be employed that may suggest themselves to those skilled in the art after reading the description, without departing from the spirit of the present disclosure and / or the scope of the appended claims. [Example]

[0045] Example 1 Synthesis of Benzotriazole Conjugate 1 N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide (CAS 107479-06-1) is added to chloroform. 1,6-Hexanediamine is added to chloroform in a 2.5:1 molar ratio of benzotriazole to diamine. The mixture is heated to approximately 40°C for approximately 4 hours. The resulting reaction mixture is concentrated using a rotary evaporator. The conjugate is purified by silica gel column chromatography. As shown in Figure 1, N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide (shown on the left, U) is reacted with Z of 1,6-hexanediamine (C) to give the conjugate C-(XU) where n=2. n is formed. This is an exemplary reaction for other compounds shown in Figure 1, where two or more Z moieties are used to create UV-absorbing linked compounds.

[0046] Example 2 Synthesis of Benzotriazole Hydrazide 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0) is dissolved in a suitable organic solvent (e.g., dichloromethane, ethyl acetate, methyl ethyl ketone). Dicyclocarbodiimide (DCC) is added to this solution in a molar ratio of approximately 1:1, and the solution is stirred for 5 minutes. An excess molar ratio of adipic acid dihydrazide is added to the stirred solution. The reaction mixture is allowed to react for 4 hours. The precipitate is removed by filtration. The solution is then extracted at least four times with acidic water to extract the remaining adipic acid dihydrazide. The resulting benzotriazole hydrazide is recrystallized from a suitable organic solvent. As shown in Figure 15, the reaction of 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid with the dihydrazide forms the conjugate U-CO-NNH2. Example 3 Synthesis of benzotriazole-HA conjugate Sodium hyaluronate (50 kDa) was added to DMSO. Benzotriazole hydrazide from Example 2 was added to the DMSO mixture at a molar ratio of hydrazide to the disaccharide unit of hyaluronic acid of 0.1:1. Dicyclocarbodiimide (DCC) was added to the hydrazide at a molar ratio of approximately 1:1. The reaction mixture was stirred overnight. Any precipitate formed was filtered, and the resulting mixture was dialyzed against water to remove DMSO. After dialysis, the contents of the dialysis bag were added to an excess of cold ethanol. The precipitated material was filtered. The precipitate was triturated with methyl ethyl ketone. The benzotriazole-HA conjugate was dried under vacuum. As shown in Figure 17, benzotriazole hydrazide (denoted U-CO-NHNH2) reacted with the carboxylic acid group of hyaluronic acid (C) to form the conjugate C-(XU). n where X is a -CO-NHNH-CO- group and n>1. This is an example reaction of other compounds shown in Figure 17, and other coupling compounds with multiple carboxylic acid groups can be used to make UV-absorbing coupling compounds. Example 4 Synthesis of benzotriazole-cellulose conjugate 1 One gram of cellulose acetate phthalate was dissolved in 50 mL of ethyl acetate:ethanol (1:1). Dicyclocarbodiimide (DCC) was added to the solution in a molar ratio of 0.9:1 to the phthalic acid groups. After stirring the solution for 5 minutes, benzotriazole hydrazide from Example 2 was added to the solution in a molar ratio of 0.8:1 to the phthalic acid groups. The reaction mixture was stirred overnight. Any precipitate formed was filtered from the solution. The resulting reaction mixture was concentrated using a rotary evaporator. The solution was poured into excess cold water to precipitate the product. The precipitate was filtered and washed with ethanol. The product was dried under vacuum. As shown in Figure 17, benzotriazole hydrazide (denoted U-CO-NHNH2) reacts with the carboxylic acid groups of cellulose acetate phthalate (C) to form the conjugate C-(XU)n. X is a -CO-NHNH-CO- group, where n>1. This is an example reaction of another compound shown in Figure 17, and other linking compounds with multiple carboxylic acid groups can be used to make UV absorbing linking compounds.

[0047] Example 5 Synthesis of Benzotriazole-Polyacrylic Acid Conjugate By adding 2 M HCl dropwise, a poly(acrylic acid sodium salt) solution (average Mw ∼1,200, 45 wt% in HO) precipitates from the solution. The precipitated poly(acrylic acid) is filtered and dried under vacuum. The poly(acrylic acid) is added to DMSO at 10% (w / v). Dicyclocarbodiimide (DCC) is added to the solution in a molar ratio of 0.9:1 to the carboxylic acid groups. After stirring the solution for 5 minutes, the benzotriazole hydrazide from Example 2 is added to the solution in a molar ratio of 0.8:1 to the carboxylic acid groups. The reaction mixture is stirred overnight. Any precipitate formed is filtered from the solution. The resulting reaction mixture is concentrated using a rotary evaporator. The solution is poured into excess cold water to precipitate the product. The precipitate is filtered and washed with ethanol. The product is dried under vacuum.

[0048] Example 6 Synthesis of partially deacetylated hyaluronic acid For a 2% (w / v) polymer solution, add 300 mL of hydrazine monohydrate to 6 g of hyaluronic acid (50 kDa). Add 3 g of hydrazine sulfate to this solution. Stir the resulting solution at 55 °C for 72-96 h. Add 120 mL of cold ethanol to the reaction mixture to precipitate the hyaluronic acid product. Filter the precipitate, wash with ethanol, and dry under vacuum for 24 h. The dried material was added to a beaker, and 100 mL of acetic acid and 60 mL of 0.5 M iodic acid (HIO3) were added to the beaker. The solution was stirred in a water bath at 4°C for at least 1 hour. Aqueous HI (57%, 17.5 mL) was added, and the mixture was stirred for 15 minutes. The solution was transferred to a separatory funnel and 150 mL of diethyl ether was added. The mixture was vigorously shaken and the aqueous layer was collected. Extraction with diethyl ether was repeated until the purple color disappeared from the organic layer. The pH of the collected aqueous solution was adjusted to 7-7.5 with 0.2 M NaOH. The polymer was precipitated by adding an excess of cold ethanol to the solution. The precipitate was filtered, washed with ethanol, and then dried under vacuum. Example 7 Synthesis of Benzotriazole-HA Conjugate 2 Partially deacetylated hyaluronic acid (Example 6) was added to DMSO. 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0) was added to the DMSO mixture at a molar ratio of 1:1 between the carboxylic acid and the amine groups of the partially deacetylated hyaluronic acid. Dicyclocarbodiimide (DCC) was added at a molar ratio of approximately 1:1 to the carboxylic acid groups. The reaction mixture was stirred overnight. Any precipitate formed was filtered, and the resulting mixture was dialyzed against water to remove DMSO. After dialysis, the contents of the dialysis bag were added to an excess of cold ethanol. The precipitated material was filtered. The precipitate was triturated with methyl ethyl ketone. The benzatriazole-HA conjugate was dried under vacuum. As shown in Figure 9, 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid was reacted with the amine group of deacetylated hyaluronic acid (C) to form the conjugate C-(XU). n where X is an amide and n>1. This is an example reaction of other compounds shown in Figure 9, and other coupling compounds with multiple amine groups can be used to make UV-absorbing coupling compounds.

[0049] Example 8 Synthesis of Benzotriazole-PEG Conjugate 1 1 g of 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0) was added to dichloromethane. Dicyclocarbodiimide (DCC) was added to the dichloromethane in a molar ratio of 1:1. After stirring the solution for 5 minutes, PEG-diamine (2,000; Sigma-Aldrich) was added to the dichloromethane in a molar ratio of carboxylic acid groups to PEG amine groups of 1.2:1. The reaction mixture was stirred overnight. Any precipitate formed was filtered from the solution. The resulting reaction mixture was concentrated using a rotary evaporator. The conjugate was purified by silica gel column chromatography. As shown in Figure 8, 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid was reacted with the amine group of PEG-diamine (C) to give conjugate C-(XU). n where n=2 and X is an amide. This is an example reaction of other compounds shown in Figure 8, and other coupling compounds having at least one amine group can be used to make UV-absorbing coupling compounds. Example 9 Synthesis of Benzotriazole-Cyclodextrin Conjugate 1 1 g of 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0) was added to DMSO. Dicyclocarbodiimide (DCC) was added to DMSO in a molar ratio of 1:1. After stirring the solution for 5 minutes, 6-monoamino-6-monodeoxy-beta-cyclodextrin hydrochloride was added to DMSO in a molar ratio of carboxylic acid groups to PEG amine groups of 1.2:1. The reaction mixture was stirred overnight. Any precipitate formed was filtered from the solution. The resulting reaction mixture was concentrated using a rotary evaporator. The conjugate was purified by silica gel column chromatography. As shown in Figure 9, 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid was reacted with the amine group of amino-cyclodextrin (C) to give conjugate C-(XU). nwhere n=1 and X is an amide. This is an example reaction of other compounds shown in Figure 9, and other coupling compounds having at least one amine group can be used to make UV-absorbing coupling compounds.

[0050] Example 10 Synthesis of benzophenone 4-hexane conjugate 1 g of benzophenone-4 (CAS 4065-45-6) was added to 50 mL of anhydrous dimethylformamide (DMF). Thionyl chloride was added to the reaction mixture so that the molar ratio of thionyl chloride to sulfonic acid groups was 0.95:1. After stirring the mixture for 4 hours, excess 1,6-hexanediamine was added (amine group:sulfonic acid group 1.2:1). The reaction was heated to 50°C and allowed to proceed overnight. The reaction mixture was poured into excess water. The precipitate was filtered, washed with water, and then dried under vacuum. As shown in Figure 12, benzophenone-4 reacted with the amine group (Z) of hexanediamine (C) to give the conjugate C-(XU). n where n=2 and X is a sulfonamide or UXCXU. This is an exemplary reaction of other compounds shown in Figure 12, and other coupling compounds having at least one amine group can be used to make UV-absorbing coupling compounds.

[0051] Example 11 Synthesis of UV-absorbing polymer 1 g of N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide and 2 g of 2-hydroxyethyl methacrylate are added to 50 mL of dimethyl sulfoxide. 300 mg of AIBN is added to the mixture. Nitrogen is bubbled through the mixture for 15 minutes. The mixture is heated to 60°C for approximately 18 hours. The mixture is added to water to precipitate the formed polymer. The polymer is dried under vacuum. As shown in Figure 10, N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide is polymerized with 2-hydroxyethyl methacrylate (A), resulting in a crystalline polymer. [ka] A polymer shown as: where DXY is the reactive residue of N-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-2-methylprop-2-enamide, where n>1, m>1, and Z=0. This is an example reaction of other compounds shown in Figure 10, and other monomers used in making UV-absorbing binding compounds. Example 12 UV-absorbing bonded particles Dissolve 1 g of hyaluronic acid in 10 mL of 0.25 M NaOH. Once dissolved, add 0.06 g of 1,4-butanediol diglycidyl ether (BDDE). Heat the mixture to 50°C for 3 hours. Add the formed gel to 500 mL of water and neutralize the solution with 0.2 M HCl. Decant the supernatant, and repeat the washing process two more times. Then, add the gel to a 60 mL syringe. Extrude the gel through a 100-mesh sieve in a filter holder. Then, extrude the gel through a 400-mesh sieve in a filter holder. Then, dry the gel under vacuum. Add the dried gel particles to 50 mL of DMSO. Add 0.1 g of benzotriazole hydrazide compound (Example 2) to the reaction mixture. Add EDC to the reaction mixture (molar ratio of EDC to hydrazide: 0.9:1). Allow the mixture to react overnight. The mixture is poured into excess water. The gel particles are filtered and dried under vacuum. The dried particles are washed with ethyl acetate and then dried under vacuum.

[0052] Example 13 Sunscreen 1 Three different sunscreen formulations are prepared using the ingredients shown in Table 1 below. [Table 1] Add water to a vessel and heat to about 75-80°C. Add the remaining ingredients of Phase A and mix with a dispersing kneader until dissolved. Add the ingredients of Phase B simultaneously and heat to about 75-80°C while mixing. Add the Phase A mixture to Phase B while mixing with a homogenizer. Cool the resulting emulsion to room temperature using a water bath with gentle stirring. Separate formulations are prepared using the UV absorbing conjugates prepared in Examples 1, 3-5, and 7-12.

[0053] Example 14 Sunscreen 2 [Table 2] Add glycerin and xanthan gum simultaneously and mix in a dispersing mixer. Then add water to the dispersed mixture. Heat the mixture to approximately 70-75°C. Add the ingredients of Phase B simultaneously and heat with mixing to approximately 70-75°C. Add Phase B to Phase A while mixing with a homogenizer. Cool the resulting emulsion to approximately 40°C using a water bath with gentle stirring. Add Phase C to the emulsion and homogenize the mixture for 2-5 minutes. Then cool the formulation to room temperature with gentle stirring.

[0054] Example 15 Sunscreen 3 [Table 3] Dermofeel® PA-3, xanthan gum, and chlorphenesin were added simultaneously. Water was then added, and the mixture was heated to approximately 80-85°C under high shear mixing. In a separate beaker, the ingredients of Phase B were added simultaneously, and the mixture was heated to approximately 80-85°C. Part B was then added to Part A under high shear mixing. The mixture was stirred for approximately 3-5 minutes. The resulting mixture was allowed to cool under medium agitation. Once the temperature was below 40°C, melitan was added. The mixture was allowed to cool to room temperature, and the pH was adjusted to 5.0-5.5, if necessary. Formulations were prepared separately using the UV-absorbing conjugates prepared in Examples 1, 3-5, and 7-12.

[0055] Example 16 1 g of sodium dodecyl sulfate was added to 100 g of deionized water. 200 mg of potassium persulfate was added to the solution. The solution was stirred at approximately 250-280 rpm. The solution was heated to approximately 40°C and stirred until the potassium persulfate dissolved. The solution was degassed using a nitrogen stream. 4.92 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole and 5.18 g of hexyl methacrylate were added to 8.55 g of toluene. The suspension was vortexed and poured into the aqueous solution. The solution was heated to approximately 70°C under a nitrogen stream. The solution was stirred for approximately 3 hours. The solution was cooled to room temperature and filtered. The sample was dried under vacuum. The NMR is shown in Figure 18. The UV spectrum of the material in dichloromethane is shown in Figure 19. Example 17 Synthesis of acid chloride derivatives The reaction glassware was dried overnight in an oven. 25.1 g of 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid (CAS 84268-36-0) was added to a round-bottom flask. 249 mL of anhydrous toluene was added to the flask using a tube and nitrogen. 1.5 mL of anhydrous DMF was added to the reaction mixture. The reaction mixture was stirred at approximately 400 rpm. 8.33 mL of thionyl chloride was added to the reaction mixture using a syringe and 18G needle. The reaction mixture was heated to 80°C for 4 hours. The reaction mixture was cooled to room temperature, and the toluene was removed under vacuum. Approximately 126 mL of hexane was added to the residue. The residue was allowed to stand overnight, and the supernatant was decanted. The precipitated material was triturated with approximately 60 mL of hexane. This was repeated five times. The sample was dried under vacuum.

[0056] Example 18 Chitosan-benzotriazole derivative 4 g of chitosan oligosaccharide (TCI) was dried under vacuum at 50°C. 102 g of anhydrous DMF was added to the chitosan. Approximately 2.2 mL of triethylamine was added to the reaction mixture. The mixture was stirred at approximately 400 rpm. 4 g of the sulfonyl chloride from Example 2 was added to the reaction mixture. The temperature was increased to 80°C, and the mixture was stirred at 200 rpm overnight. The reaction mixture was cooled to room temperature. Approximately 200 mL of water (pH 8.3) was added to the reaction mixture. The solution was stirred until a precipitate formed. The precipitate was centrifuged and the supernatant was decanted. This process was repeated four times. Water / methanol (60 / 40 v / v) was added to the precipitate to wash it. After centrifugation, the supernatant was decanted. This process was repeated with methanol. The precipitate was dried under vacuum. The NMR is shown in Figure 20. The UV spectrum of the material in dichloromethane is shown in Figure 21. Another aspect of the present invention may be as follows. [1] A topical formulation composition comprising one or more UV-absorbing linked compounds containing a UV-absorbing compound linked to a linked compound, wherein the UV-absorbing compound is a benzophenone compound linked to the linked compound via a sulfonamide linker, the benzophenone linked compound having a molecular weight of at least 800 daltons; a benzimidazole compound linked to the linked compound via a sulfonamide linker, the benzimidazole linked compound having a molecular weight of at least 800 daltons; a benzotriazole compound linked to the linked compound via an amide linker, the benzotriazole linked compound having a molecular weight of at least 800 daltons; or a benzotriazole linked compound linked to the linked compound via a Michael addition reaction product. 1. A topical formulation comprising a UV-absorbing compound selected from the group consisting of a benzotriazole compound conjugated to a polysaccharide, the benzotriazole conjugated compound having a molecular weight of at least 800 Daltons; a benzotriazole-functionalized polymer having a molecular weight of at least 800 Daltons, wherein the benzotriazole is conjugated to the polymer as a methacrylate, acrylate, or acrylamide derivative of the benzotriazole compound; and a benzotriazole compound conjugated to a polysaccharide, the benzotriazole-polysaccharide conjugated compound having a molecular weight of at least 800 Daltons, wherein the UV-absorbing conjugated compound is not transported through or absorbed by the skin. [2] The UV absorbing compound is (UX) n -C, In the formula, U is a UV absorbing compound moiety, X is a thioether, amine, amide, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, and n is an integer, n≧1. [3] The UV absorbing compound is (UX) n -C, The composition according to [1], wherein U is a UV absorbing compound moiety, X is an ester, C is a linking compound moiety, and n is an integer, and n≧1. [4] The UV absorbing compound has the structure: [C1] JPEG0007789659000011.jpg2947 and The composition according to [1] above, wherein Y is a UV absorbing compound moiety; X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-; D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group; A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer; B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A; n is an integer, n≧1; m and z are integers, m≧0, z≧0. [5] The composition according to [4], wherein the UV absorbing binding compound is a block copolymer or a random copolymer. [6] The UV absorbing compound is (UX) n -C-(X-U1) m and In the formula, U is a UV absorbing compound moiety, U1 is a UV absorbing compound moiety having a chemical structure different from U, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, C is a linking compound moiety, and n and m are each integers, and n and m are ≧1. [7] The UV absorbing compound is [C2] JPEG0007789659000012.jpg3166 and wherein Y is a UV absorbing compound moiety, Y1 is a UV absorbing compound moiety having a chemical structure different from Y, X is a thioether, amine, amide, ester, urethane, sulfonamide group, or -CO-NH-NH-CO-, D is a residue of a vinyl, acrylate, methacrylate, or acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n and p are each integers, n and p are ≧1, m and z are each integers, m≧0, z≧0, and the structure of formula (4) may be a block copolymer or a random copolymer. [8] The composition according to [7], wherein the UV absorbing binding compound is a block copolymer or a random copolymer. [9] The composition according to [1], wherein the UV absorbing compound comprises a benzophenone-based compound, a benzotriazole-based compound, or a benzimidazole-based compound having an absorbance in the range of about 200 to about 380 nm.

[10] The composition according to [9], wherein the UV-absorbing binding compound comprises one or more UV-absorbing benzotriazole compounds having a reactive residue of an acrylamide group, an acrylate group, a methacrylate group, a maleimide group, an acrylonitrile group, or a vinyl sulfone group.

[11] The topical formulation of [1], which is formulated as a sunscreen formulation comprising a daily use sunscreen, a water-resistant sunscreen, or a combination thereof, wherein the cosmetic formulation comprises a moisturizer, foundation, lipstick, lip gloss, chapstick, concealer, highlighter, blush, eye shadow, makeup remover, toner, serum, anti-aging product, fixative spray, or a combination thereof, and the hair product composition comprises a shampoo, conditioner, leave-in conditioner, hair mousse, hair gel, hair spray, curl cream, hair wax, treatment oil, medicated hair treatment, or a combination thereof.

Claims

1. A topical formulation composition comprising one or more UV-absorbing binding compounds containing a UV-absorbing compound bound to a binding compound, wherein the UV-absorbing binding compound is a benzotriazole-functionalized polymer having a molecular weight of at least 800, the benzotriazole being bound to the polymer as an acrylamide derivative of the benzotriazole compound, and the UV-absorbing binding compound is not transported through or absorbed by the skin; the UV absorbing bonded compound has the formula (UX) n -C; A topical formulation composition wherein U is a UV absorbing compound, X is an amide, C is a linking compound, and n is an integer, n≧1.

2. The UV absorbing binding compound has the structure: 【Chemistry 1】 and 2. The composition of claim 1, wherein Y is a UV-absorbing compound, X is an amide, D is a residue of an acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n is an integer and n≧1, m and z are each integers and m≧0, z≧0, and the UV-absorbing binding compound is a block copolymer or a random copolymer.

3. The UV absorbing compound is (U-X) n -C-(X-U1) m and 2. The composition of claim 1, wherein U is a UV absorbing compound, U1 is a UV absorbing compound having a chemical structure different from U, X is an amide, C is a linking compound, and n and m are each integers, and n and m are ≧1.

4. The UV absorbing binding compound is 【Chemistry 2】 and 10. The composition of claim 1, wherein Y is a UV absorbing compound, Y1 is a UV absorbing compound having a chemical structure different from Y, X is an amide, D is a residue of an acrylamide group, A is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer, B is a residue of a vinyl, acrylate, methacrylate, or acrylamide monomer different from A, n and p are each integers, n and p are ≧1, m and z are each integers, m≧0, z≧0.

5. The composition of claim 4 , wherein the UV absorbing binding compound is a block copolymer or a random copolymer.

6. The composition of claim 1 , wherein the UV absorbing compound has an absorbance in the range of 200 to 380 nm.

7. 10. The composition of claim 1 or 6, wherein the UV absorbing binding compound comprises one or more UV absorbing benzotriazole compounds containing the reactive residue of an acrylamide group.

8. The composition of claim 1 formulated as a sunscreen formulation, a cosmetic formulation, or a hair product composition.

9. The composition of claim 8, wherein the sunscreen formulation is an everyday sunscreen, a water-resistant sunscreen, or a combination thereof.

10. The composition of claim 8, wherein the cosmetic formulation is a moisturizer, foundation, lipstick, lip gloss, chapstick, concealer, highlighter, blush, eye shadow, makeup remover, toner, serum, anti-aging product, fixing spray, or a combination thereof.

11. The composition of claim 8, wherein the hair product composition is a shampoo, conditioner, leave-in conditioner, hair mousse, hair gel, hair spray, curl cream, hair wax, treatment oil, medicated hair treatment, or a combination thereof.

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