Cosmetic composition containing DRAGLINE SPIDER SILK

Abstract

Cosmeceutical compositions containing MaSp (major ampullate spidroin protein)-based fibers are disclosed. Also disclosed are articles containing the compositions.

Description

[Technical Field]

[0001] Cross-references to related applications This application is a direct reference to U.S. Patent Provisional Application No. 63 / 014,444, filed on April 23, 2020, with the entire contents of the following patents: U.S. Patent Provisional Application No. 63 / 048,135, filed on July 5, 2020, with the entire contents of the following patents: U.S. Patent Provisional Application No. 63 / 144,089, filed on February 1, 2021, with the entire contents of the following patents: U.S. Patent Provisional Application No. 63 / 079,621, filed on September 17, 2020, with the entire contents of the following patents:048,135, filed on July 5, 2020, with the entire contents of the following patents: U.S. We claim priority under Section 119(e) of U.S. Patent No. 63 / 134,343 of "SILK," filed on January 6, 2021.

[0002] Technical field In some embodiments, the present invention aims to provide compositions containing a protein derived from MaSp (major ampullate spidroin protein), and to provide the preparation and use of the said protein as an antimicrobial substance. [Background technology]

[0003] Dragline spider silk is known in the field as the silk used by spiders that build orb webs to construct the frame and radius of their webs, which serve as a good lifeline in case of falls or encounters with danger. To enable these tasks, dragline fibers exhibit remarkably high toughness due to a combination of high elasticity and strength, and are considered the strongest fibers, whether naturally occurring or artificially created. For example, dragline is six times stronger than high-tensile steel in its diameter and three times stronger than Kevlar, one of the strongest synthetic fibers ever created.

[0004] Spidroins, often referred to as MaSp (major ampullate spidroins) 1 and 2, and ADF-3 and ADF-4 in Araneus diadematus, consist of two major polypeptides. These proteins have apparent molecular weights ranging from 200 to 720 kDa, depending on the sample lifetime and analytical conditions. Known spidroins consist of remarkably repeating blocks that modify alanine-rich segments to form crystalline β-sheets and glycine-rich segments that are more flexible and lack a more ordered structure in the fiber. This C-terminal region is non-repeating, remarkably conserved across species, and adopts an α-helix conformation. Furthermore, the N-terminal region of spidroin proteins has been found to be remarkably conserved between different spindolons and between different spider species. [Overview of the Initiative]

[0005] In one embodiment, a medicated cosmetic composition comprising a medicated cosmetic effective amount of a complex containing derivatized porous MaSp (major ampullate spidroin protein) fiber bound to metal oxide particles, The derivatized porous MaSp fiber comprises at least 10 m 2 Characterized by a BET surface area of ​​ / g, The derivatized porous MaSp-based fiber contains a functional moiety that covalently binds to tyrosine of the porous MaSp-based fiber, The functional moiety contains a polymer and a metal oxide chelate group, The metal oxide particles are bound to the derivatized porous MaSp-based fiber via the metal oxide chelate group. There is a pharmaceutical cosmetic composition.

[0006] In one embodiment, the pharmaceutical cosmetic composition further comprises a cosmetically acceptable carrier.

[0007] In one embodiment, the pharmaceutical cosmetic composition is characterized as a sunscreen composition.

[0008] In one embodiment, the pharmaceutically cosmetically effective amount is 10 (w / w)% to 50 (w / w)% of the complex in the composition.

[0009] In one embodiment, the pharmaceutical cosmetic composition is characterized as a hair color composition.

[0010] In one embodiment, the metal oxide particles are selected from titania, zirconia, silica, or any combination thereof.

[0011] In one embodiment, the metal oxide particles are characterized by a particle size of 10 to 5,000 nm.

[0012] In one embodiment, the w / w ratio of the derivatized porous MaSp-based fiber in the composition to the metal oxide particles is 0.01 to 100.

[0013] In one embodiment, the polymer contains polyglutaraldehyde (PGA), and the w / w ratio of the polymer to the porous MaSp-based fiber is 0.001 to 5.

[0014] In one embodiment, the functional moiety is covalently bound to the side chain of the tyrosine via a diazo bond, a silyl group, or any combination thereof.

[0015] In another aspect, there is a pharmaceutical cosmetic composition comprising a pharmaceutically effective amount of derivatized porous MaSp-based fibers bound to a dye or pigment, where the derivatized porous MaSp-based fibers are characterized by a BET surface area of at least 10 m 2 / g, where the derivatized porous MaSp-based fibers contain a functional moiety that covalently binds to the tyrosine of the porous MaSp-based fibers, where the functional moiety contains an amino, carboxy, nitro, sulfonate, carbonyl, ester, anhydride, carbonate ester, carbamate, cyano, hydroxy, polymer, or any combination thereof, and there is a pharmaceutical cosmetic composition.

[0016] In one embodiment, the polymer is a cationic polymer selected from the group consisting of polyethyleneimine (PEI), polylysine, polyaniline, or any combination thereof.

[0017] In one embodiment, the effective amount includes the w / w concentration of the derivatized porous MaSp-based fibers in the pharmaceutical cosmetic composition, which is 20 (w / w)% to 99.9%.

[0018] In one embodiment, the functional moiety is covalently bound to the side chain of the tyrosine via a diazo bond, a silyl group, or any combination thereof.

[0019] The pharmaceutical cosmetic composition is characterized by a pH value of 3 to 7.

[0020] In one embodiment, the pharmaceutical cosmetic composition further comprises a cosmetically acceptable carrier, and the composition is a pharmaceutical cosmetic composition, a hair color composition, or both.

[0021] In one embodiment, the pharmaceutical cosmetic composition is characterized by a positive zeta potential and is suitable for binding to the hair of a subject that requires it.

[0022] In another embodiment, a medicated cosmetic composition comprising porous MaSp (major ampullate spidroin protein) fibers bound to a cosmetic active ingredient, wherein the porous MaSp fibers are at least 10m 2 There exists a medicinal cosmetic composition characterized by a BET surface area of ​​1 / g.

[0023] In one embodiment, the w / w concentration of the cosmetic active ingredient in the composition is 1 to 80%, and the w / w ratio between the cosmetic active ingredient and the porous MaSp fiber is 10:1 to 1:10.

[0024] In one embodiment, the release rate of the cosmetic active ingredient from the medicated cosmetic composition is reduced by at least 10% compared to the control.

[0025] In one embodiment, the medicinal cosmetic composition further comprises one of 1 to 95 (w / w)% of a solvent, a film-forming agent, and a thickening agent.

[0026] In one embodiment, the composition is characterized by a viscosity of 50 to 3000 cP at 25°C.

[0027] In one embodiment, the medicated cosmetic comprises a cosmetically acceptable carrier, and the composition is formulated for application to the skin or hair of a subject requiring it.

[0028] In one embodiment, the MaSp fiber is characterized by a decomposition temperature (Td) of 280°C to 350°C, as determined by differential scanning calorimetry (DSC).

[0029] In one embodiment, the MaSp fiber has a glass transition temperature (T) of 200°C to 250°C determined by DSC. g ) is a characteristic feature.

[0030] In one embodiment, the MaSp fiber is given by formula 1 0: (X1) Z X2GPGGYGPX3X4X5GPX6GX7GGX8GPGGPGX9X 10The amino acid sequence shown is (In the formula, X1 is independently A or G at each position, Z is an integer from 5 to 30, X2 is S or G, X3 is G or E, X4 is G, S, or N, X5 is Q or Y, X6 is G or S, X7 is P or R, X8 is Y or Q, X9 is G or S, X 10 It includes an iterative region containing S or G.

[0031] In another embodiment, there is a method for reducing or preventing UV-related damage to a subject, comprising the step of applying an effective amount of the medicated cosmetic composition of the present invention to the skin of the subject to reduce or prevent UV-related damage to the subject.

[0032] In another embodiment, there is a method for coloring hair, which includes the step of coloring the hair by bringing an effective amount of the medicinal cosmetic composition of the present invention into contact with at least a portion of the hair under appropriate conditions.

[0033] In one embodiment, suitable conditions include a pH of less than 9.

[0034] In another embodiment, there is a method for supplementing a target with a cosmetic active ingredient, which includes the step of supplementing the target with the cosmetic active ingredient by administering the medicinal cosmetic composition of the present invention to the target.

[0035] In one embodiment, the method is for reducing or preventing damage to (i) the skin of the subject, (ii) the hair of the subject, or both of (i) and (ii), the damage relating to exposure to conditions selected from UV irradiation, thermal radiation, environmental pollutants, oxidizing agents, reducing agents, irritants, or any combination thereof.

[0036] In one embodiment, the method is for skin rejuvenation, skin moisturizing, skin conditioning, wrinkle reduction, skin relaxation, hair coloring, and hair shaping, or any combination thereof, and the method enhances or prolongs the stability of the cosmetic active ingredient, the enhancement or prolongation being at least 10% greater compared to the cosmetic active ingredient in its original state.

[0037] Unless otherwise defined, all technical and / or chemical terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention relates. Similar or equivalent methods and materials may be used in the practice or testing of embodiments of the present invention, although exemplary methods and / or materials are described below. In the event of any inconsistency, this specification, including definitions, shall prevail. Furthermore, materials, methods, and examples are merely illustrative and not necessarily intended to be limiting.

[0038] Further embodiments and the full scope of the availability of the present invention will become apparent from the detailed description provided herein. However, the detailed description and specific examples, while representing preferred embodiments of the present invention, are provided merely as examples, as various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from the detailed description. [Brief explanation of the drawing]

[0039] [Figure 1A-B] Figures 1A and 1B are SEM images of healthy human hair (Figure 1A) versus damaged human hair (Figure 1B) treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated MaSp fibers (SVX). The aminated MaSp fibers (SVX) preferably bind to the damaged area of ​​the human hair, resulting in nearly complete coverage (Figure 1B). [Figure 2]Figure 2 is a bar graph showing the effect of heat exposure on the tensile strength of human hair treated with an exemplary hair composition of the present invention (Formula with SVX) containing 1-10 (w / w)% aminated MaSp fibers, compared to untreated hair (unprotected) and hair treated with a carrier (Formula w / oSVX). The results show superior tensile strength of human hair treated with the exemplary hair composition of the present invention after 200 heat treatments at 220°C compared to the control. [Figure 3] Figure 3 is a bar graph showing the effect of heat exposure on the moisture content of human hair treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated SVX fibers, compared to untreated hair. The results show superior moisture retention of human hair treated with the exemplary hair composition of the present invention after 200 heat treatments at 220°C, compared to the control. [Figure 4] Figure 4 is a bar graph showing the tensile strength of human hair treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated SVX fibers, compared to untreated hair after exposure to seawater or chlorinated water. This result shows superior tensile strength compared to human hair treated with the exemplary hair composition of the present invention after 3 days of exposure to the sea / pool. [Figure 5A-B] Figures 5A and 5B are bar graphs (Figure 5B) and images (Figure 5A) showing the pollution repellent effect of human hair (3, 6, 9) treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated SVX fibers versus untreated hair (1, 4, 7) and hair treated with a carrier (2, 5, 8) after exposure to environmental pollutants (e.g., carbon black). The results show superior pollution repellent effect compared to the control of human hair treated with the exemplary hair composition of the present invention. [Figure 6A-B]Figures 6A and 6B are bar graphs showing the color retention of human hair treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated SVX fibers versus untreated hair after exposure to seawater (Figure 6B) or chlorinated water (Figure 6A). Hair samples treated with the composition of the present invention showed only minimal fading, while the control showed nearly five times more fading. [Figure 7] Figure 7 is an image showing the color retention of human hair treated with an exemplary hair composition of the present invention containing 1-10 (w / w)% aminated SVX fibers versus untreated hair after 7 days of exposure to UV irradiation. SVX provides protection against UV light and free radicals (derived from UV irradiation). Day 0 shows colored hair that has not been exposed to UV light. [Figure 8] Figure 8 is an image illustrating the hair straightening effect of human hair treated with an exemplary hair composition of the present invention containing 5 (w / w)% aminated SVX fibers versus untreated hair. The SVX coating on the hair straightens the hair even without requiring further heat and chemical treatment. [Figure 9] Figure 9 is a bar graph showing the curl effect of human hair treated with an exemplary hair composition of the present invention containing approximately 0.5 (w / w)% aminated SVX fibers versus human hair treated with commercially available compositions (Croda MFP, Croda CP, PVP, RevCare). Untreated hair was used as a negative control. As shown in the graph, the hair composition of the present invention is characterized by increased retention of hair curl over time compared to commercially available compositions and the untreated control. [Figure 10] Figure 10 is an image illustrating the curl effect of human hair treated with an exemplary hair composition of the present invention containing approximately 0.5 (w / w)% of original MaSp fibers (SVX) versus untreated hair. Coating of curled hair with SVX enhances the curl design even without requiring further heat treatment. [Figure 11]Figure 11 is a graph showing the chemical stability of retinol encapsulated in an exemplary composition of the present invention containing approximately 0.5 (w / w)% of the original MaSp fiber (SVX) after exposure to an oxidizing agent (H2O2), compared to a commercially available formulation. Retinol encapsulated with SVX is more stable and resistant to the oxidizing agent compared to the control. [Figure 12] Figure 12 is a graph showing the chemical stability of retinol encapsulated in an exemplary composition of the present invention containing approximately 0.5 (w / w)% of the original MaSp fiber (SVX) after exposure to UV irradiation, compared to a commercially available formulation. Retinol encapsulated with SVX is more stable and resistant to UV irradiation compared to the control. [Figure 13] Figure 13 is a graph showing the skin retention time of retinol encapsulated in an exemplary composition of the present invention containing approximately 1 (w / w)% of original MaSp fibers (SVX), compared to commercially available retinol formulations. Retinol encapsulated with SVX remained more stable compared to unprotected retinol. [Figure 14A-B] Figures 14A and 14B show images illustrating the reduction of skin wrinkles in skin treated with an exemplary composition of the present invention containing approximately 10 (w / w)% original MaSp fibers (SVX) and a film-forming agent (Figure 14B) compared to untreated skin (Figure 14A). [Figure 15A-C] Figures 15A-C are depth diagrams showing the reduction of skin wrinkles in skin treated with an exemplary composition of the present invention containing approximately 10 (w / w)% of original MaSp fibers (SVX) and a film-forming agent at 15 minutes (Figure 15B) and 60 minutes (Figure 15C), compared to untreated skin (Figure 15A). [Figure 16]Figure 16 illustrates contaminant protection of skin models treated with exemplary compositions of the present invention containing approximately 1 (w / w)% original MaSp fibers (SVX) compared to an untreated control. A: 100 mg of the formulation (formulations containing and without SVX) was spread homogeneously on a polyurethane skin model; B: 3 mg / cm2 of carbon particles were applied to the surface. The contaminant particles showed little adhesion to SVX; C: The surface was washed five times under running water, followed by a thorough washing cycle and gentle scrubbing. [Figure 17] Figure 17 is a graph showing the moisture retention of skin treated with an exemplary composition of the present invention containing approximately 1 (w / w)% original MaSp fibers (SVX), as analyzed by transepidermal water loss (TEWL) measurement, compared to untreated skin (w / o SVX). TEWL analysis indicates that applying a thin layer of the demonstration formulation containing SVX to the skin can prevent transepidermal water loss and help reduce the appearance and / or presence of dry, scaly, and dull skin. [Figure 18A-B] Figures 18A and 18B are images illustrating irritation tests performed by applying various irritants to skin treated with an exemplary composition of the present invention containing approximately 1 (w / w)% of original MaSp fibers (SVX), compared to untreated skin. [Figure 19A-D] Figures 19A-D are SEM images of MaSp-based fibers (SVX). Figures 19A and 19B show images of porous fibers. Figures 19C and 19D show images of non-porous particles. [Figure 20] Figure 20 is a graph showing the release of hyaluronic acid (HA) from SVX-E fibers compared to cellulose and silk. This graph shows HA-specific peaks and SVX-E / silk / cellulose-specific peaks (Y axis) versus wash cycles (X axis). [Figure 21A-C] Figures 21A-21C are graphs showing the release of acids from SVX-E fibers compared to a control, as determined by the tape strip test. Figure 21A shows the release of lactic acid (LA). Figure 21B shows the release of glycolic acid (GA). Figure 21C shows the release of hyaluronic acid (HA). [Figure 22A-B] Figures 22A and 22B are graphs showing the release of retinyl acetate (RA) and glycerol from SVX-E fibers compared to the control. [Figure 23] Figure 23 is a graph showing the zeta potentials of amination-modified MaSp fibers (Amine), carboxylated MaSp fibers (Acid), PAA-modified amination-modified MaSp fibers (PAA), PEI-modified carboxylated MaSp fibers (PEI), and the original MaSp fiber (SVXE). [Figure 24A-B] Figures 24A and 24B are SEM images of porous MaSp fibers conjugated with polyacrylate (Figure 24A) or polyglutaraldehyde (Figure 24B). [Figure 25A-B] Figures 25A and 25B are SEM images of PEI-modified porous MaSp fibers applied to human hair under acidic conditions of pH 3 to 5 (Figure 25A) and basic conditions of pH 10.5 (Figure 25B). [Figure 26] Figures 26A and 26B are SEM images (at different magnifications) of amination (via 4-(2-aminoethyl)aniline (APEA)) MaSp fibers applied to human hair under acidic conditions of pH=3.5. [Figure 27A-B] Figures 27A and 27B show SEM images (at different magnifications) of amination (via 3-aminopropyl triethoxysilane (APTES)) MaSp fibers applied to human hair under acidic conditions of pH=3.5. [Modes for carrying out the invention]

[0040] The present invention relates, in some embodiments thereof, to hair color compositions comprising chemically modified MaSp fibers bound to a dye or pigment. As described herein below, the inventors have successfully implemented hair color compositions comprising various derivatized porous MaSp fibers. Some of these hair color compositions resulted in a uniform and stable coating of hair after contact between the hair (e.g., human hair) and the hair color composition. Exemplary hair color compositions that have successfully implemented hair coating include, but are not limited to, those comprising amination of MaSp fibers (e.g., MaSp fibers chemically modified with 4-(2-aminoethyl)aniline, 3-aminopropyl(amonipropyl)triethoxysilane, and / or polyethyleneimine, PEI).

[0041] The present invention relates, in some embodiments thereof, to a sunscreen composition comprising metal oxide (e.g., titania) nanoparticles complexed with chemically modified MaSp fibers. Exemplary sunscreen compositions, though not limited to them, include titania nanoparticles bound to MaSp fibers chemically modified with salicylic acid covalently bonded to a polymer such as polyglutaraldehyde (PGA). Dispersion of titanium dioxide nanoparticles complexed with salicylates bound to PGA-derivativeized MaSp fibers exhibits superior sunscreen properties compared to the original MaSp fibers.

[0042] The present invention relates, in some embodiments thereof, to a medicated cosmetic composition comprising non-derivativeized MaSp fibers bound to cosmetic active ingredients such as hyaluronic acid (HA) and retinyl acetate (RA). Exemplary medicated cosmetic compositions of the present invention exhibited slow release of HA and RA from the composition compared to rapid release from silk and cellulose fibers. Furthermore, the exemplary medicated cosmetic compositions of the present invention enable longer retention times of various cosmetic ingredients on the skin surface and improve the biological stability of the cosmetic ingredients.

[0043] In one aspect, the present invention provides derivatized porous MaSp (major ampullate spidroin protein) - based fibers comprising functional moieties covalently bound to the amino acids of the porous MaSp - based fibers. In some embodiments, the porous MaSp - based fibers are characterized by a BET surface area of at least 10 m 2 / g. In some embodiments, the porous MaSp - based fibers are as described later herein.

[0044] In some embodiments, the derivatized porous MaSp - based fibers comprise functional moieties covalently bound to the side chains of the amino acids of the porous MaSp - based fibers, and the porous MaSp - based fibers are characterized by a BET surface area of at least 10 m 2 / g.

[0045] In some embodiments, the derivatized porous MaSp - based fibers comprise functional moieties covalently bound to the side chains of the amino acids of the porous MaSp - based fibers, and the porous MaSp - based fibers are characterized by (i) a BET surface area of at least 10 m 2 / g; (ii) a decomposition temperature of 280 - 350 °C; (iii) a glass transition point of 200 - 250 °C, and (iv) an amino acid sequence comprising repeating regions each independently having the following formula 10 As shown or at least one of the combinations of (i), (ii), (iii), and (iv).

[0046] In some embodiments, the derivatized porous MaSp - based fibers comprise functional moieties covalently bound to the side chains of the amino acids of the porous MaSp - based fibers, and the porous MaSp - based fibers comprise repeating regions each independently having the following formula 10 As shown The derivatized porous MaSp - based fibers are characterized by (i) a BET surface area of at least 10 m 2 / g; (ii) a decomposition temperature of 280 - 350 °C; (iii) a glass transition point of 200 - 250 °C, or at least one of the combinations of (i), (ii), and (iii). In some embodiments, the terms "porous MaSp - based fibers" and "MaSp - based fibers" are used interchangeably herein.

[0047] In some embodiments, the functional moiety is covalently bonded to an amino acid of a porous MaSp fiber. In some embodiments, the functional moiety is covalently bonded to an amino acid selected from tyrosine, serine, cysteine ​​and lysine, threonine, histidine, arginine, aspartic acid and glutamic acid, or any combination thereof. In some embodiments, the functional moiety is covalently bonded to the side chain of an amino acid selected from tyrosine, serine, cysteine ​​and lysine, threonine, histidine, arginine, aspartic acid and glutamic acid, or any combination thereof. In some embodiments, the functional moiety is covalently bonded to the side chain of tyrosine, serine, cysteine ​​and lysine, or any combination thereof. In some embodiments, the functional moiety is covalently bonded to the side chain of tyrosine (e.g., a phenol ring).

[0048] In some embodiments, the derivatized porous MaSp fiber of the present invention includes a functional moiety covalently bonded to at least one tyrosine side chain via a diazo bond, a silyl group, or both. In some embodiments, the derivatized porous MaSp fiber of the present invention includes diazotized tyrosine, silylated tyrosine, or both. In some embodiments, 1-99%, 10-99%, 10-90%, 10-80%, 10-70%, and 10-60% (including any range or value between them) of the tyrosine residues (or side chains) in the derivatized porous MaSp fiber of the present invention are diazotized and / or silylated.

[0049] In some embodiments, the derivatized porous MaSp fibers of the present invention include a functional moiety covalently bonded to the side chain of at least one tyrosine via a diazo bond, which is also referred to herein as "diazotized tyrosine". In some embodiments, the diazotized tyrosine is a diazo bond: [ka] It contains a functional moiety covalently bonded to the phenyl ring of tyrosine via [a specific linkage].

[0050] In some embodiments, the functional portion is covalently bonded to the porous MaSp fiber via one of the following: diazo, silyl, carbonyl, amide, ester, maleimide, or any combination thereof.

[0051] In some embodiments, the functional moiety is covalently bonded to at least one tyrosine residue of the porous MaSp fiber. In some embodiments, the functional moiety is covalently bonded to at least one tyrosine residue via a bond selected from diazo, silyl, ester, carbamate, carbonyl, (O- or S)-thiocarbamate, or any combination thereof. In some embodiments, the functional moiety is covalently bonded to at least one tyrosine residue via a diazo bond. In some embodiments, the functional moiety is covalently bonded to at least one tyrosine residue via a linker containing any of the reactive groups capable of (i) forming a diazo bond with the phenol ring of tyrosine (e.g., an alkyldiazonium group or an aryldiazonium group) and / or (ii) forming a Si-C bond with the phenol ring of tyrosine (e.g., an alkoxysilyl or halosilyl).

[0052] In some embodiments, the composition substantially lacks functional moieties and / or polymers adsorbed onto MaSp fibers.

[0053] In some embodiments, the derivatized porous MaSp fiber of the present invention, which includes a functional moiety covalently bonded to the MaSp fiber via a diazo bond, is represented by formula I: [ka] (In the formula, [ka] A represents a MaSp fiber, A is selected from substituted or unsubstituted aryls (e.g., phenyl, or bicyclic / condensed aromatic rings, e.g., naphthalene), heteroaryls (e.g., C5-6 aromatic rings containing 1, 2, 3, or 4 heteroatoms selected from O, N, and S), and alkyls (e.g., linear or branched alkyls of C1-10), R is a functional part of the present invention or comprises such a part, and a dashed line represents a linker (or spacer) as described herein.

[0054] In some embodiments, the derivatized porous MaSp fiber of the present invention, which includes a functional moiety covalently bonded to the MaSp fiber via a silyl group, is represented by formula 2: [ka] (wherein the formula, the dashed line and R are as described herein, and each R1 independently comprises one of the following: hydrogen, optionally substituted alkyl (e.g., C1-10 linear or branched alkyl), hydroxyl, or alkoxy (e.g., C1-10 alkoxy)).

[0055] In some embodiments, the functional moiety of the present invention comprises one of the following: a hydroxyl group, a mercapto group, an amino group, a carboxylate group, a nitro group, a sulfonate group, a carbonyl group, an anhydride, a carbonate ester, a carbamate group, a nitrile group, and a polymer or any combination thereof. In some embodiments, the functional moiety comprises a hydroxyl group, a mercapto group, an amino group, a carboxylate group, and a polymer or any combination thereof. In some embodiments, the functional moiety is covalently bonded to an amino acid of a porous MaSp fiber via a linear or branched linker. In some embodiments, a derivatized amino acid of a porous MaSp fiber comprises one or more functional moieties covalently bonded thereto.

[0056] In some embodiments, the functional portion of the present invention is bound to a tyrosine residue via a diazoaryl linker. In some embodiments, the functional portion of the present invention is bound to a diazoaryl linker. In some embodiments, the terms “linker” and “spacer” are used interchangeably herein.

[0057] In some embodiments, the functional moiety (or R) comprises an electrophilic and / or nucleophilic group. Many electrophiles and nucleophiles are well known in the art.

[0058] Non-limiting examples of electrophilic reactive groups include, but are not limited to, aldehydes, ketones, carboxyls, esters, imines, oximes, acylhalides, active esters (e.g., N-hydroxysuccinimid), chloroformates, anhydrides, epoxides, isocyanates, nitros, sulfonates, trialkylammoniums, and halos, or any combination thereof, including any alkyl and / or aryl derivative (e.g., carboxyalkyl, carboxyaryl, alkylcarbonyl, haloalkyl, haloaryl, etc.).

[0059] Non-exclusive examples of nucleophilic reactive groups include, but are not limited to, hydroxy, mercapto, amino, phosphine, or any combination thereof.

[0060] In some embodiments, the functional moiety comprises multiple electrophilic and / or nucleophilic groups. In some embodiments, the functional moiety comprises a polyamine (e.g., linear polyamines, e.g., spermine or spermidine; or branched polyamines, e.g., tris(2-aminoethyl)amine). In some embodiments, the functional moiety comprises a polyol (e.g., pentaerythritol, xylitol). In some embodiments, the functional moiety comprises a di or tricarboxylic acid (e.g., citric acid, malic acid, succinic acid).

[0061] In some embodiments, the functional moiety (or R) is protected by an amine protecting group selected from alkyl (e.g., C1-10 linear or branched alkyl, e.g., methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl), C1-10 alkoxy (e.g., methoxy, ethoxy, propoxy, osyloxy), vinyl group (e.g., vinyloxy), C1-10 alkylamino (e.g., methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino), (e.g., Fmoc, Boc, benzyl, CBz, etc.) ) comprising any one of the following: protected amines, hydroxy (optionally protected by a hydroxy protecting group such as tert-butyl or trimethylsilyl), mercapto (optionally protected by a thiol protecting group), silyl, siloxane (e.g., trialkoxysilane), nitro, sulfonate, cyano, halo, trialkylammonium, aldehyde, ketone, ketone, carboxy, ester, imine, oxime, acylhalides, active esters (e.g., N-hydroxysuccinimid), chloroformates, anhydrides, epoxides, isocyanates, or any combination thereof.

[0062] In some embodiments, the linker (or spacer) comprises an alkyl which may be optionally substituted with any one of the following: carboxy, halo, hydroxy, amino, cycloalkyl, alkyl, nitro, sulfonate, cyano, or any combination thereof or derivatives. In some embodiments, the linker comprises an alkoxy, thioalkyl, aminoalkyl, glycol, or any combination thereof which may be optionally substituted. In some embodiments, alkyls comprising any derivative thereof are described later herein. In some embodiments, the linker comprises a disubstituted alkyl (e.g., aminohexanoic acid) or a disubstituted heteroalkyl group. In some embodiments, the linker comprises C1-C10 alkyl, C1-C10 aminoalkyl, C1-C10 alkoxy, C1-C10 mercaptoalkyl, carbonyl derivatives (e.g., -C(O)NH-, -C(O)O-, -C(O)-, -C(O)S-, -C(NH)NH-, -C(NH)O-, -C(NH)S-), and optionally includes one or more heteroatoms (e.g., S, N, O) or any combination thereof in the linker skeleton.

[0063] In some embodiments, the linker (or spacer) comprises natural and / or unnatural amino acids, alkyl, amide bonds, ester bonds, and thioester bonds, urea bonds (including any derivative or combination thereof). In some embodiments, the linker of the present invention comprises a click reaction product (a covalent product such as a cyclization reaction, and / or a succinimide-thioether moiety formed via a click reaction). Further linkers or spacers are well known in the art.

[0064] Click reactions are well known in this field and include, in particular, Michael addition of maleimides and thiols (resulting in succinimide-thioether addition); azido-alkynecyclo addition; Diels-Alder reactions (e.g., direct and / or inverse electron-demanded Diels-Alder); dibenzylcyclooctin 1,3-nitrone (or azido)cyclo addition; and photoclick reactions of alkenetetrazoles.

[0065] The term “heteroalkyl,” as used herein, refers to an alkyl group as defined herein, in which one or more of the constituent carbon atoms are replaced by nitrogen, oxygen, or sulfur. In some embodiments, the heteroalkyl group may be further substituted with alkoxy groups with one, two, three, or four substituents as described herein. Examples of heteroalkyl groups are polyglycols or polyalkoxylates, such as polyethylene glycol.

[0066] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described herein: [ka] (In the formula, The dashed line represents a linker, which is as described herein. In some embodiments, R is as described herein. In some embodiments, the linker is or comprises a C1-6 or C1-10 alkyl group, which may be optionally substituted. In some embodiments, R comprises an amino, halo, nitro, carbonyl, ester, or carboxyl group.

[0067] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described herein: [ka] (In the formula, R is as described herein; n, m, and o are each an integer from 0 to 20, and each R2 is independently H, or halogen, -NO2, -CN, -OH, -CONH2, -CONR2, -CNNR2, -CSNR2, -CONH-OH, -CONH-NH2, -NHCOR, -NHCSR, -NHCNR, -NC(=O)OR, -NC(=O)NR, -NC(=S)OR, -NC(=S)NR, -SO2R, -SOR, -SR, -SO2OR, -SO2N(R)2, -NHNR2, -NNR, C1-C6 haloalkyl, C1-C6 alkyl which may be optionally substituted, -NH2, -NH(C1-C6 alkyl), -N(C1- X1 is a substituent selected from or including C6alkyl)2, C1-C6alkoxy, C1-C6haloalkoxy, hydroxy(C1-C6alkyl), hydroxy(C1-C6alkoxy), alkoxy(C1-C6alkyl), alkoxy(C1-C6alkoxy), C1-C6alkylNR2, C1-C6alkylSR, -CONH(C1-C6alkyl), -CON(C1-C6alkyl)2, CO2H, CO2R, -OCOR, -OCOR, -OC(=O)OR, -OC(=O)NR, -OC(=S)OR, -OC(=S)NR, or a combination thereof; X1 is a heteroatom (e.g., O, S, N, NH) or absent). In some embodiments, n, m, and o are each independently integers ranging from 0 to 20, 1 to 20, 1 to 3, 3 to 5, 5 to 7, 7 to 10, 10 to 15, and 15 to 20 (including any range between them). In some embodiments, R is an amino, carboxy, [ka] , or a combination thereof, including, where X1 is as described herein, and R3 is H, C1-C which may be optionally replaced. 10The alkyl group is an optionally substituted aryl group, an optionally substituted heteroaryl group, or any combination thereof, or includes such a group. In some embodiments, X1 is N or NH, or includes such a group. In some embodiments, R2 is H, or an optionally substituted C1-C6 alkyl group, or includes such a group.

[0068] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described below herein: [ka] (In the formula, n, R2, and R3 are as described herein.

[0069] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described below herein: [ka] (wherein R2 and n are as described above in this specification).

[0070] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described below herein: [ka] (wherein R and n are as described herein, and each R1 independently is hydrogen, alkyl (e.g., C1-C6 alkyl or C1-C 10 Alkyl), hydroxy, or C1-C 10 (Containing any one of the following alkoxys: methoxy, ethoxy, propoxy, pentoxy, etc.).

[0071] In some embodiments, the derivatized porous MaSp fibers of the present invention are as described below herein: [ka] (wherein R1, n, R3, and R2 are as described herein).

[0072] In some embodiments, the functional moiety is covalently bonded to histidine, arginine, aspartic acid, glutamic acid, or any combination thereof. Those skilled in the art will understand that the functional moiety may be covalently bonded to the carboxyl side chain via amino-, hydroxy-, or mercapto-substituted linkers.

[0073] In some embodiments, the derivatized porous MaSp fibers are as described below in this specification: [ka] (wherein X represents a heteroatom of the side chain selected from O, S, and N, and R is as described above herein). In some embodiments, X represents a heteroatom of any one of the amino acids of the MaSp fiber.

[0074] In some embodiments, the derivatized porous MaSp fibers are as described below in this specification: [ka] (In the formula, X represents a heteroatom of any one side chain of an amino acid in the MaSp fiber, [ka] ∫ represents the binding site of the MaSp fiber to an amino acid, the wavy line represents the linker, and R is as described herein. In some embodiments, R includes amino, halo, nitro, carbonyl, ester, or carboxy.

[0075] In some embodiments, the functional portion is covalently bonded to the hydroxyl group of at least one tyrosine residue of the MaSp fiber.

[0076] In some embodiments, the derivatized porous MaSp fibers are as described below in this specification: [ka] (wherein X is as described herein).

[0077] In some embodiments, the functional moiety is covalently bonded to at least one amino acid of the MaSp fiber via a silyl bond. In some embodiments, the amino acid is a nucleophilic amino acid (e.g., serine, cysteine, threonine, and lysine). In some embodiments, the derivatized porous MaSp fiber is as described herein below: [ka] (In the formula, X represents a heteroatom (e.g., S, NH, or O) of any one side chain of an amino acid in the MaSp fiber.) [ka] The ∫ represents a bond point to the MaSp fiber, the wavy bond represents a linker, and R is as described herein, with each R1 independently comprising one of hydrogen, alkyl, hydroxy, or alkoxy.

[0078] In some embodiments, the derivatized porous MaSp fibers are as described below in this specification: [ka] (In the formula, X represents a heteroatom of any one side chain of an amino acid in the MaSp fiber, [ka] (where represents a binding site to the MaSp fiber). In some embodiments, X represents a heteroatom of the cysteine ​​and / or tyrosine side chain.

[0079] In some embodiments, the derivatized porous MaSp fibers are as described below in this specification: [ka] (wherein X represents a heteroatom selected from O, S, and N, and R is as described above herein).

[0080] In some embodiments, the functional moiety is covalently bonded to the MaSp fiber via at least one nucleophilic amino acid selected from serine, cysteine, threonine, and lysine. In some embodiments, the functional moiety is covalently bonded to the nucleophilic amino acid of the MaSp fiber via a bond selected from silyl, ester, carbamate, carbonyl, (O- or S)-thiocarbamate, or a combination thereof.

[0081] In some embodiments, the functional portion provides reactivity to the MaSp fiber. Those skilled in the art understand that the functional portion, such as an amine, can react with an electrophile (e.g., a haloalkyl or ester). Thus, by introducing the functional portion into the MaSp fiber, the MaSp fiber can subsequently react with any reagent (e.g., a small molecule or polymer) that is reactive to the functional portion. In some embodiments, the functional portion induces or increases the reactivity of the MaSp fiber. In some embodiments, the functional portion induces or increases the reactivity of the MaSp fiber to any reagent that can react with it.

[0082] In some embodiments, the derivatized porous MaSp fibers of the present invention include a functional moiety (e.g., amino or carboxy) covalently bonded to a polymer. In some embodiments, the polymer is covalently bonded to the functional moiety via a functional group that is reactive to the functional moiety (e.g., the functional moiety is or contains carboxy, and the functional group of the polymer is amino, mercapto, or hydroxy, or the functional moiety is or contains amino, and the functional group of the polymer is halo, carbonyl, or carboxy). Those skilled in the art will understand that there are further well-known reactive groups that can be used for covalent bonding of the polymer to the functional moiety of the present invention (e.g., via click reactions). In some embodiments, the polymer is covalently bonded to the functional moiety via any of -C(O)NH-, -C(O)O-, -C(O)-, -C(O)S-, -C(NH)NH-, -C(NH)O-, -C(NH)S-, -NC(O)-, -N(C)-, or a combination thereof.

[0083] In some embodiments, the functional portions of the derivatized porous MaSp fibers are covalently bonded to the polymer. In some embodiments, the polymer is positively and / or negatively charged. In some embodiments, the polymer is neutral.

[0084] In some embodiments, the polymer is selected from cationic polymers (e.g., PEI, polylysine, polyarginine, chitosan) (including any derivatives and / or copolymers thereof), anionic polymers (e.g., PAA), and / or nonionic polymers (e.g., PVA, PVC, silane, polyamide). Other cationic polymers, anionic polymers, and / or nonionic polymers are well known in the art.

[0085] In some embodiments, the polymer is selected from the group consisting of polyglutaraldehyde (PGA), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylate, polyethyleneimine (PEI), polyacrylamide (PAAm), polylysine, polyarginine, polyaniline, polyurethane, polyamide (e.g., nylon), polyvinyl chloride, polysilane, chitosan, N-haramine polymer, N-haramid polymer, polysilane co-polyolefin, silane-crosslinked polyolefin, and polyvinylpyrrolidone (PVP) (including any combination or copolymer thereof). In some embodiments, the polymer is a linear polymer. In some embodiments, the polymer is a branched polymer. In some embodiments, the polymer is a copolymer. In some embodiments, the polymer is a graft copolymer.

[0086] In some embodiments, the polymer is covalently bonded to a nucleophilic or electrophilic functional group of the derivatized porous MaSp fiber. Those skilled in the art understand that amination of MaSp fibers can react with a carboxyl group of a polymer (e.g., PAA) or a carbonyl group of a polymer (e.g., PGA) to obtain derivatized MaSp fibers covalently bonded to the polymer. Furthermore, carboxylated MaSp fibers can react with an amino group of a polymer (e.g., PET) or a hydroxyl group of a polymer (e.g., PVA). The inventors have successfully synthesized conjugates of derivatized MaSp fibers (including functional groups bonded to the tyrosine of the MaSp fiber via diazo bonds or silyl groups, as described above) with various polymers, e.g., PGA, PAA, PVA, PEI, PAAm, or combinations thereof (e.g., PGA-co-PEI). Furthermore, the inventors have successfully synthesized the above conjugates using MaSp proteins having mutant amino acid sequences (also referred to herein as "mutant MaSp proteins").

[0087] The inventors have successfully synthesized derivatized MaSp fibers modified with PAAm via in situ polymerization of amination-MaSp fibers represented by formula 3: [ka] In some embodiments, PAAm-modified derivatized MaSp fibers are as follows: [ka] (wherein each n is independently 0-10, 0-20, 1-20, 1-3, 3-5, 5-7, 7-10, 10-15, 15-20 (including any range between them)). In some embodiments, m is 1-10000, 1-10, 10-100, 100-1000, 1000-10000 (including any range between them).

[0088] In some embodiments, the w / w ratio between the MaSp fiber and polymer is 0.01:1 to 1:1, 0.02:1 to 1:1, 0.05:1 to 1:1, 0.09:1 to 1:1, 0.1:1 to 1:1, 0.5:1 to 1:1, or 0.9:1 to 1:1 (including any range in between).

[0089] In some embodiments, the w / w ratio between MaSp fibers and polymers is 100:1~1:100, 95:1~1:100, 80:1~1:100, 60:1~1:100, 50:1~1:100, 30:1~1:100, 20:1~1:100, 10:1~1:100, 9:1~1:100, 5:1~1:100, 2:1~1:100, 100:1~1:80, 95:1~1:80, 80:1~1:80, 60:1~1:80, 50:1~1:80, 30:1~1:80, 20:1~1:80, 10:1~1:80, 9:1~1:80, 5:1~1:80 , 2:1~1:80, 100:1~1:50, 95:1~1:50, 80:1~1:50, 60:1~1:50, 50:1~1:50, 30:1~1:50, 20:1~1:50, 10:1~1:50, 9:1~1:50, 5:1~1:50, 2:1~1:50, 100:1~1:10, 95:1~1:10, 80:1~1:10, 60:1~1:10, 50:1~1:10, 30:1~1:10, 20:1~1:10, 10:1~1:10, 9:1~1:10, 5:1~1:10, or 2:1~1:10 (including any range in between).

[0090] In some embodiments, the functional groups of the derivatized MaSp fibers are bonded to a polymer containing multiple reactive groups. In some embodiments, these include nucleophilic groups (e.g., amino, hydroxy, thiol), electrophilic groups (e.g., carbonyl, carboxy, ester, succinimide ester, halo, nitro, and azide), or both. In some embodiments, MaSp fibers bonded to a polyaldehyde polymer (e.g., polyglutaraldehyde) are represented by formula 4: [ka] (In the formulas, dashed lines represent optional combinations, and m and n are integers.) In some embodiments, each n is independently 0-10, 0-20, 1-20, 1-3, 3-5, 5-7, 7-10, 10-15, 15-20 (including any range between them). In some embodiments, m is 1-10000, 1-10, 10-100, 100-1000, 1000-10000 (including any range between them).

[0091] In some embodiments, the derivatized MaSp fibers are bonded to a polymer containing multiple chelating agents. In some embodiments, the chelating agents include (i) a metal chelating group that can bond to a metal or a salt thereof, (ii) a metal oxide chelating group, or both (i) and (ii).

[0092] In some embodiments, the metal chelating group can form a complex with a metal or a salt thereof (via a coordination bond).

[0093] In some embodiments, the metal or its salts include transition metals. Non-limiting examples of fiber metals include, but are not limited to, gold (Au), copper (Cu), palladium (Pd), zinc (Zn), aluminum (Al), tungsten (W), titanium (Ti), silicon (Si), zirconium (Zr), hafnium (Hf), tin (Sn), gallium (Ga), molybdenum (Mo), nickel (Ni), vanadium (V), platinum (Pt), tantalum (Ta), germanium (Ge), and niobium (Nb), or any combination thereof.

[0094] In some embodiments, the metal chelating group includes thiols, amines, phenols, and carboxyls (including derivatives thereof). In some embodiments, the metal chelating group includes crown ethers. In some embodiments, the metal chelating group is a cyclic molecule comprising multiple carboxyl and / or hydroxyl groups configured for complex formation with a metal or a salt thereof. In some embodiments, metal chelating groups including DOTA, NOTA, NODA, EDTA, and HBED-CC (including salts, derivatives, or combinations thereof) are well known in the art. In some embodiments, the metal chelating group includes iminodiacetic acid (IDA), its salts, or derivatives.

[0095] In some embodiments, polymers containing multiple metal chelate groups are represented below in this specification: [ka] (In the formula, CM represents the chelating agent, k is in the range of 10-10000, 10-100, 100-1000, and 100-10000 (including any range in between); m is in the range of 0-10, 0-3, 3-5, and 5-10 (including any range in between); and each n independently represents an integer in the range of 0-10, 0-20, 1-20, 1-3, 3-5, 5-7, 7-10, 10-15, and 15-20 (including any range in between)).

[0096] In another embodiment, the derivatized MaSp fiber comprises a functional moiety (e.g., a polymer) bonded to a metal oxide chelate group, the functional moiety as described herein. In some embodiments, the metal oxide chelate group has an affinity for metal oxides or particles containing them. In some embodiments, the metal oxide chelate group can form complexes with metal oxides or particles containing them (e.g., via coordination bonds). In some embodiments, the metal oxide particles are as described herein.

[0097] In some embodiments, the term “complexing with ~” refers to the stable (e.g., chemically stable) complex formation of a metal and / or metal oxide (including any particles containing them). In some embodiments, stable complex formation refers to the property of a metal-bonded derivatized MaSp fiber (also referred to herein as “complex” or “stable complex”) that retains at least 60%, at least 70%, at least 80%, at least 95%, or at least 99% of the initial metal content after exposure to a solvent (e.g., organic solvent, aqueous solvent, etc.) or storage under atmospheric conditions for a period of at least 1 month (m), at least 2 m, at least 6 m, at least 12 m, at least 2 years (y), at least 3 y, at least 10 y (including any range in between).

[0098] In some embodiments, the weight / weight (w / w) ratio of the functional portion in the derivatized fiber of the present invention to the porous MaSp fiber is 0.01-30%, 0.01-0.1%, 0.1-0.5%, 0.5-1%, 1-5%, 5-10%, 10-20%, 20-30% (including any range in between).

[0099] In some embodiments, the functional moiety filling in the derivatized MaSp fibers is 0.01 μmol / g to 10 mmol / g, 0.01 μmol / g to 0.1 μmol / g, 0.1 μmol / g to 0.5 μmol / g, 0.5 μmol / g to 1 μmol / g, 1 μmol / g to 10 μmol / g, 10 μmol / g to 30 μmol / g, 30 μmol / g to 50 μmol / g, 50 μmol / g to 100 μmol / g, 100 μmol / g to 500 μmol / g, 0.5 to 1 mmol / g, 1 to 5 mmol / g, 5 to 10 mmol / g (including any range in between).

[0100] In some embodiments, at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 80%, at least 90%, at least 95%, and at least 99% (including any range in between) of the tyrosine residues in the derivatized MaSp fiber of the present invention are replaced with functional moieties as described herein. In some embodiments, the degree of substitution of tyrosine residues in the derivatized MaSp fiber is 1-99%, 1-5%, 5-10%, 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, and 90-99% (including any range in between).

[0101] In some embodiments, the derivatized MaSp fiber of the present invention includes a functional moiety covalently bonded to at least one tyrosine side chain such that the degree of substitution of tyrosine residues (or side chains) in the derivatized MaSp system is 1-90%, 1-99%, 10-99%, 10-90%, 10-80%, 10-70%, or 10-60% (including any range or value between these).

[0102] In some embodiments, the degree of tyrosine residue (or side chain) substitution in the derivatized MaSp fibers ranges from up to 90%, 80%, 70%, 65%, and 60% (including any range in between). The inventors have successfully substituted up to approximately 60% of tyrosine residues (or side chains) using various functional moieties (some of which are described in the Examples section).

[0103] In some embodiments, the functional moiety is selectively bound to at least one tyrosine residue of the MaSp fiber. In some embodiments, the selectivity includes at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, and at least 99% (including any range in between).

[0104] In some embodiments, the functional portion provides a positive and / or negative charge to the MaSp fiber. In some embodiments, the functional portion modifies the surface charge of the MaSp fiber. In some embodiments, the functional portion modifies the properties of the MaSp fiber, which are selected from hydration, water contact angle, dispersion, or solubility (e.g., solubility in water and / or organic solvents).

[0105] In some embodiments, derivatized (e.g., amino-derivatized) porous MaSp fibers are characterized by a positive zeta potential value of 1 to 50 at a pH of about 7. As illustrated herein, amination-MaSp fibers are characterized by a positive zeta potential value of about 20 at a pH of about 7, while unmodified MaSp fibers have a positive zeta potential value of about -20 at a pH of about 7.

[0106] In some embodiments, derivatized (e.g., amino-derivatized) porous MaSp fibers have a zeta potential value that is at least 50%, at least 70%, at least 100%, at least 150%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% higher than that of unmodified porous MaSp fibers.

[0107] In some embodiments, derivatized (e.g., carboxy-derivatized) porous MaSp fibers are characterized by a zeta potential of -20 to -100 at a pH of about 7. As illustrated herein, carboxylated MaSp fibers are characterized by a zeta potential value of about -40 at a pH of about 7, while unmodified MaSp fibers have a zeta potential value of about -20 at a pH of about 7.

[0108] In some embodiments, derivatized (e.g., carboxy-derivatized) porous MaSp fibers have a zeta potential value at least 50%, at least 70%, at least 100%, at least 150%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% lower than that of unmodified porous MaSp fibers. Those skilled in the art understand that the exact zeta potential value varies depending on the pH and the load (i.e., w / w ratio) of functional groups in the porous MaSp fibers.

[0109] In some embodiments, the derivatized MaSp fibers retain the porosity of the original (e.g., non-derivativeized) MaSp fibers. In some embodiments, the derivatized MaSp fibers are at least 10 m 2 It is characterized by a BET surface area of ​​ / g.

[0110] SEM images of the derivatized MaSp-based fibers are shown in Figures 3A and 3B. As shown in Figures 3A and 3B, the derivatized MaSp-based fibers exhibit remarkable porosity (e.g., at least 10m). 2 The porosity (defined by the BET surface area per gram) is sequence-independent, because MaSp proteins and mutant MaSp proteins exhibit a remarkably porous structure. Furthermore, the porosity of derivatized MaSp fibers is substantially retained compared to that of unmodified MaSp fibers.

[0111] In some embodiments, the derivatized porous MaSp fibers of the present invention include a functional moiety covalently bonded to one or a combination thereof of a polymer, a linker, and a chelate moiety. In some embodiments, the functional moiety is covalently bonded to a linker as described herein. In some embodiments, the functional moiety is covalently bonded to a chelate moiety, which is one of a metal chelate group, a metal oxide chelate group, or a combination thereof, as described herein.

[0112] The inventors have successfully implemented the PEI and / or amino-modified derivatized fibers of the present invention with hair color compositions containing various dyes, as described in the Examples section.

[0113] In some embodiments, the composition of the present invention comprises the derivatized porous MaSp fiber of the present invention and optionally further components selected from further polymers, dyes, and / or pigments.

[0114] In some embodiments, the composition comprises MaSp fibers in amounts of 0.01-50(w / w)%, 0.01-1(w / w)%, 1-5(w / w)%, 5-10(w / w)%, 10-15(w / w)%, 15-20(w / w)%, and 20-50(w / w)% (including any range in between) and further components.

[0115] In some embodiments, this simple is 0.001~95(w / w)%, 0.005~95(w / w)%, 0.009~95(w / w)%, 0.01~95(w / w)%, 0.05~95(w / w)%, 0.09~95(w / w)%, 0.1~95(w / w)%, 0.5~95(w / w)%, 0.9~95(w / w)%, 1~95(w / w)%, 5~95(w / w) / w)%, 10~95(w / w)%, 15~95(w / w)%, 20~95(w / w)%, 30~95(w / w)%, 50~95(w / w)%, 0.01~80(w / w)%, 0.05~80(w / w)%, 0.09~80(w / w)%, 0.1~80(w / w)%, 0.5~80(w / w)%, 0.9~80(w / w)%, 1~80(w / w)%, 5~ 80(w / w)%, 10~80(w / w)%, 15~80(w / w)%, 20~80(w / w)%, 30~80(w / w)%, 50~80(w / w)%, 0.001~50(w) / w)%, 0.005~50(w / w)%, 0.009~50(w / w)%, 0.01~95(w / w)%, 0.01~50(w / w)%, 0.05~50(w / w)%, 0.0 The material contains derivatized porous MaSp fibers in the following concentrations: 9-50(w / w)%, 0.1-50(w / w)%, 0.5-50(w / w)%, 0.9-50(w / w)%, 1-50(w / w)%, 5-50(w / w)%, 10-50(w / w)%, 15-50(w / w)%, 20-50(w / w)%, or 30-50(w / w)%, (including any range in between).

[0116] In some embodiments, the composition of the present invention essentially consists of the derivatized porous MaSp fibers of the present invention and further components optionally described herein. In some embodiments, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 99% by weight, and at least 99.9% by weight (including any range in between) of the composition consists of the derivatized porous MaSp fibers of the present invention and further components optionally described herein.

[0117] In some embodiments, the derivatized porous MaSp fiber essentially consists of any one of the derivatized porous MaSp fibers described herein. In some embodiments, the derivatized porous MaSp fiber of the present invention substantially lacks further fibers (e.g., derivatized fibers) and / or further polymers and / or further organic or inorganic substances or particles.

[0118] In some embodiments, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 99% by weight, and at least 99.9% by weight (including any range in between) of the derivatized porous MaSp fiber of the present invention consists of any one of the derivatized porous MaSp fibers described herein.

[0119] In some embodiments, the derivatized porous MaSp fibers and / or compositions of the present invention are stable. In some embodiments, the derivatized porous MaSp fibers of the present invention are considered stable if the derivatized fibers retain their physical and / or chemical properties and / or are chemically and / or physically stable after dispersion in solution and / or after long-term storage under atmospheric storage conditions and / or after thermal exposure to temperatures up to 300°C, up to 200°C, up to 100°C, up to 80°C, and up to 60°C (including any range in between).

[0120] In some embodiments, the compositions of the present invention are considered stable if the derivatized porous MaSp fibers of the present invention are stably bound to further components (for example, the compositions are chemically stable after dispersion in solution and / or after long-term storage under atmospheric storage conditions and / or with respect to thermal exposure to temperatures up to 300°C, 200°C, 100°C, 80°C, and 60°C (including any range in between)).

[0121] In some embodiments, atmospheric conditions include exposure to any one of the inert chemicals, such as solvents (organic solvents and / or aqueous solvents (where the solvent is inert, i.e., has no chemical reactivity with any of the components of the composition)); thermal exposure to temperatures up to 300°C, 200°C, 100°C, 80°C, and 60°C (including any range in between); exposure to UV / vis irradiation (and / or electromagnetic irradiation, IR irradiation, microwave irradiation, etc.); and exposure to moisture and / or atmospheric gases. In some embodiments, atmospheric conditions include repeated exposure to inert chemicals. In some embodiments, atmospheric conditions include exposure to temperatures below the melting point and / or decomposition point of any of the components of the composite (e.g., MaSp fibers or derivatized MaSp fibers). Those skilled in the art will understand that the precise definition of atmospheric storage conditions may include further parameters or conditions well known in the art.

[0122] In some embodiments, the compositions and / or derivatized porous MaSp fibers of the present invention are considered stable if they substantially maintain their structure and their physical properties (e.g., mechanical stability, porosity, tensile strength, etc.) and chemical properties (hydration, zeta potential, hydrophobic / hydrophilic, reactivity), and / or if further components maintain contact with or bond to the derivatized MaSp fibers of the present invention (e.g., are not substantially degraded).

[0123] In some embodiments, the compositions and / or derivatized porous MaSp fibers of the present invention are considered chemically stable if their chemical composition is substantially maintained.

[0124] In some embodiments, the compositions and / or derivatized MaSp fibers of the present invention are substantially chemical and / or physically stable for at least one month (m), at least two m, at least six m, at least twelve m, at least two years (y), at least three y, at least ten y (including any range in between), as substantially described herein. In some embodiments, the compositions and / or derivatized MaSp fibers of the present invention are substantially stable under atmospheric storage conditions for the periods described herein.

[0125] In some embodiments, derivatized (e.g., amino-derivatized) porous MaSp fibers are characterized by a positive zeta potential value of 1 to 50 at a pH of about 7. As illustrated herein, amination-MaSp fibers are characterized by a positive zeta potential value of about 20 at a pH of about 7, while unmodified MaSp fibers have a zeta potential value of about -20 at a pH of about 7.

[0126] In some embodiments, derivatized (e.g., amino-derivatized) porous MaSp fibers have a zeta potential value that is at least 50%, at least 70%, at least 100%, at least 150%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% higher than that of unmodified porous MaSp fibers.

[0127] In some embodiments, derivatized (e.g., carboxy-derivatized) porous MaSp fibers are characterized by a zeta potential value of -20 to -100 at a pH of about 7. As illustrated herein, carboxylated MaSp fibers are characterized by a zeta potential value of about -40 at a pH of about 7, and unmodified MaSpk fibers have a zeta potential value of about -20 at a pH of about 7.

[0128] In some embodiments, derivatized (e.g., carboxy-derivatized) porous MaSp fibers have a zeta potential value at least 50%, at least 70%, at least 100%, at least 150%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% lower than that of unmodified porous MaSp fibers. Those skilled in the art understand that the exact zeta potential value varies depending on the pH and the load (i.e., w / w ratio) of functional groups in the porous MaSp fibers.

[0129] In some embodiments, the derivatized porous MaSp fibers of the present invention include a functional moiety covalently bonded to one or a combination thereof of a polymer, a linker, and a chelate moiety. In some embodiments, the functional moiety is covalently bonded to a linker as described herein. In some embodiments, the functional moiety is covalently bonded to a chelate moiety, which is one of a metal chelate group, a metal oxide chelate group, or a combination thereof, and the metal chelate group and metal oxide chelate group are as described herein.

[0130] In some embodiments, the derivatized porous MaSp fibers of the present invention include dyes or pigments bonded to a functional moiety, which are as described herein. In some embodiments, the dyes or pigments are bonded to the functional moiety via covalent or non-covalent bonds. In some embodiments, the dyes or pigments are bonded to the functional moiety via hydrogen bonds, van der Waals interactions, electrostatic interactions, van der Waals interactions, electrostatic interactions, pp stacking, or any combination thereof.

[0131] Non-exclusive examples of dyes include, but are not limited to, anionic dyes (e.g., Congo Red, Alizarin Pure Blue B, Acid Red 88, Trypan Blue), cationic dyes (e.g., methine dyes, anthraquinone dyes, azo dyes, Coomassi, Methylene Blue), and neutral dyes (e.g., Neutral Orange RL, Neutral Red GRL, Neutral Gray 2BL), Brilliant Carmine 6B, Lake Red C, Watching Red, Diazo Yellow, Hansa Yellow, Phthalocyanine Blue, Phthalocyanine Green, Alkali Blue, and Aniline Black, or any combination thereof. Other neutral or charged organic dyes are well known in the field.

[0132] In some embodiments, the pigments used are classified by their Color Index Generic Name or Color Index Constitution Number. These numbers may be preceded by CI.

[0133] In some embodiments, the pigment is a yellow pigment, and is, for example, but is not limited to, CI Pigment Yellows 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 155, 167, 172, or 18.

[0134] In some embodiments, the pigment is a magenta pigment, and is, for example, but is not limited to, CI Pigment Reds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48(Ca), 48(Mn), 57(Ca), 57:1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, or 245.

[0135] In some embodiments, the pigment is a purple pigment, for example, CI Pigment Violets 19, 23, 32, 33, 36, 38, 43, or 50.

[0136] In some embodiments, the pigment is a cyan pigment comprising, but not limited to, CI Pigment Blues 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66; or CI Vat Blues 4 and 60.

[0137] Examples of pigments other than magenta, cyan, and yellow include, but are not limited to, CI Pigment Greens 7 and 10; CI Pigment Browns 3, 5, 25, and 26; and CI Pigment Oranges 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, and 63.

[0138] In some embodiments, the w / w ratio between MaSp fibers and dyes or pigments is 0.01:1 to 10:1, 0.01:1 to 0.05:1, 0.05:1 to 0.1:1, 0.1:1 to 0.2:1, 0.2:1 to 0.3:1, 0.3:1 to 0.4:1, 0.4:1 to 0.5:1, 0.5:1 to 0.7:1, 0.7:1 to 0.9:1, 0.5:1 to 1:1, 0.9:1 to 1:1, 1:1 to 1.5:1, 1.5:1 to 2:1, 2:1 to 3:1, 3:1 to 5:1, 5:1 to 7:1, 7:1 to 10:1, 10:1 to 30:1, 30:1 to 50:1, 50:1 to 100:1 (including any range in between).

[0139] In some embodiments, the dye or pigment is adsorbed onto a derivatized porous MaSp fiber.

[0140] In some embodiments, the dye or pigment is stably bound to the derivatized porous MaSp fibers. In some embodiments, the composition containing the dye or pigment bound to the derivatized porous MaSp fibers is stable after repeated washing (for example, retaining at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of its color intensity).

[0141] In some embodiments, the composition of the present invention is a coating composition.

[0142] In some embodiments, a composition comprising a dye or pigment bound to a derivatized porous MaSp fiber is used to coat a substrate. In some embodiments, the porous MaSp fiber facilitates adhesion or binding to the substrate. In some embodiments, the substrate is one of a glass substrate, a polymer substrate, or a metal substrate. In some embodiments, the substrate includes body tissue. In some embodiments, the substrate is one of skin, hair, nails, or any combination thereof.

[0143] In some embodiments, the substrate is a charged substrate. In some embodiments, a composition comprising a dye or pigment bound to derivatized porous MaSp fibers reduces the degradation of the dye or pigment (e.g., chemical degradation and / or physical degradation) compared to a control. In some embodiments, the control comprises a coating composite lacking derivatized porous MaSp fibers.

[0144] complex In another embodiment, there is a composite comprising the derivatized porous MaSp fibers of the present invention bonded to a metal, a metal salt, metal oxide particles, or any combination thereof. In some embodiments, the metal oxide particles are bonded to the derivatized porous MaSp fibers via coordination bonds, electrostatic interactions, or both.

[0145] In some embodiments, the composite of the present invention comprises a derivatized porous MaSp fiber of the present invention bonded to a metal, a metal component selected from metal salts, or metal oxide particles, or a combination thereof, wherein the metal component exists in the form of particles or separate atoms, and is in an elemental state or an oxidized state. In some embodiments, the metal component comprises a metal and / or a metal salt, and the metal component comprises a first metal and / or a second metal of the present invention.

[0146] In some embodiments, the composite of the present invention comprises a derivatized porous MaSp fiber of the present invention bonded to a metal component described herein via one or more chelating agents of the present invention.

[0147] In some embodiments, the metal component is coordinately (i.e., via coordination bonds or complex formation) bonded to the derivatized MaSp fiber via one or more chelating agents of the present invention, and one or more chelating agents of the present invention are covalently bonded to the functional portion of the present invention (e.g., the polymer described herein). In some embodiments, the composite of the present invention comprises the derivatized porous MaSp fiber of the present invention bonded to the metal component, and the derivatized porous MaSp fiber comprises a plurality of chelating agents covalently bonded to the polymer described herein. In some embodiments, the chelating agents are as described herein above (e.g., (i) a metal chelating group that can bond to a metal or a salt thereof, (ii) a metal oxide chelating group, or both).

[0148] In some embodiments, the composite of the present invention comprises metal oxide particles bound to derivatized porous MaSp fibers via a chelating agent. In some embodiments, the chelating agent is a metal oxide chelating group as described herein. In some embodiments, the metal oxide particles are complexed with the chelating agent. In some embodiments, the metal oxide particles are stably bound to the derivatized porous MaSp fibers (for example, the composite is chemically stable after dispersion in solution and / or after storage under long-term atmospheric storage conditions and / or after thermal exposure to temperatures up to 300°C, 200°C, 100°C, 80°C, and 60°C (including any range in between)).

[0149] In some embodiments, atmospheric conditions include exposure to any one of the inert chemicals, such as solvents (organic solvents and / or aqueous solvents (where the solvent is inert, i.e., unreactive with any of the components of the complex)); thermal exposure to temperatures up to 300°C, 200°C, 100°C, 80°C, and 60°C (including any range in between); exposure to UV / vis irradiation (and / or electromagnetic irradiation, IR irradiation, microwave irradiation, etc.); and exposure to moisture and / or atmospheric gases, etc. In some embodiments, atmospheric conditions include repeated exposure to inert chemicals. In some embodiments, atmospheric conditions include exposure to temperatures below the melting point and / or decomposition point of any of the components of the complex (e.g., MaSp fibers or derivatized MaSp fibers). Those skilled in the art will understand that a precise definition of atmospheric storage conditions may include further parameters or conditions well known in the art.

[0150] In some embodiments, the composite of the present invention is considered stable if it maintains its structure and its physical properties (e.g., mechanical stability, porosity, tensile strength, electrical conductivity, etc.) and chemical properties (hydration, zeta potential, hydrophobic / hydrophilic, reactivity), and / or if the metal component maintains contact or bonding with the derivatized MaSp-based fibers of the present invention (e.g., substantially not decomposed (substantially as described herein)).

[0151] In some embodiments, the complex of the present invention is considered chemically stable if the complex substantially maintains its chemical composition.

[0152] In some embodiments, the composites of the present invention are substantially chemical and / or physically stable for at least 1 month (m), at least 2 m, at least 6 m, at least 12 m, at least 2 years (y), at least 3 y, and at least 10 y (including any range in between), substantially as described herein. In some embodiments, the composites of the present invention are substantially stable under atmospheric storage conditions for the periods described herein.

[0153] In some embodiments, the composite of the present invention comprises derivatized MaSp fibers of the present invention that are doped with a metal component. In some embodiments, the metal component is homogeneously distributed within the composite (for example, on or within the porous nanofibers).

[0154] In some embodiments, the metal oxide is selected from the group consisting of titanium oxide, aluminum oxide, iron(II / III) oxide, zirconium oxide, zinc oxide, silicon oxide, or a mixture thereof. In some embodiments, the metal oxide chelating group has affinity and / or selectivity for titanium oxide. In some embodiments, the chelating agent has affinity and / or selectivity for metal oxide particles. In some embodiments, the chelating agent has affinity and / or selectivity for titanium oxide particles. In some embodiments, the metal oxide particles are as described above herein.

[0155] In some embodiments, the derivatized porous MaSp fiber includes a functional moiety covalently bonded to a metal oxide chelate group. In some embodiments, the metal oxide chelate group is covalently bonded to the functional moiety via a linker as described herein. In some embodiments, the metal oxide chelate group is covalently bonded to the functional moiety via a PGA linker. In some embodiments, each PGA chain is covalently bonded to multiple metal oxide chelate groups.

[0156] In some embodiments, the functional portion of a derivatized porous MaSp fiber covalently bonded to a metal oxide chelate group is represented as follows: [ka] (In the equation, the dashed line represents an arbitrarily chosen combination, where each n is an independent integer between 1 and 10000).

[0157] In some embodiments, the metal oxide chelate group comprises a carboxyl group and / or a hydroxyl group. In some embodiments, the metal oxide chelate group comprises a small molecule and / or a polymer. In some embodiments, the metal oxide chelate group is a monodentate, bidentate, tridentate, and tetradentate ligand. In some embodiments, the ligand-containing metal oxide chelate group has affinity and / or selectivity for titania. In some embodiments, the metal oxide chelate group comprises a ligand comprising one or more carboxylic acid groups and optionally one or more hydroxyl groups. In some embodiments, the metal oxide chelate group comprises a ligand, a cyclic and polydentate ligand, or a linear ligand.

[0158] In some embodiments, the metal oxide chelate group is a polymer containing carboxyl side chain groups and / or hydroxyl side chain groups (e.g., PVA, polyacrylate, polyglycolate, etc. (including mixtures or copolymers thereof)).

[0159] Non-exclusive examples of metal oxide chelating groups include, but are not limited to, salicylic acid, phosphonic acid, hydroxamic acid, malonic acid, pyrogallol, 5-hydroxy-1,4-naphthoquinone, quinones, or any combination thereof. Other metal oxide chelating groups with affinity for titania are well known in this field.

[0160] In some embodiments, the metal oxide chelating group comprises an oxidized tyrosine side chain (e.g., dihydroxyphenyl or quinone). In some embodiments, the derivatized MaSp fiber comprises at least one oxidized tyrosine residue (e.g., a tyrosine residue in the form of dihydroxyphenyl or quinone). Those skilled in the art will understand that oxidized tyrosine can be obtained, for example, by reacting the MaSp fiber with tyrosinase to obtain at least a portion of the oxidized tyrosine residues (e.g., in the form of dihydroxyphenyl or quinone).

[0161] In some embodiments, the metal oxide chelate group is bonded to the polymer described herein. In some embodiments, the metal oxide chelate group is covalently bonded to the polymer described herein. In some embodiments, the chelate moiety is covalently bonded to the functional group of the derivatized MaSp fiber.

[0162] In some embodiments, the composite of the present invention comprises a derivatized porous MaSp fiber containing a plurality of metal oxide chelating groups bonded thereto, wherein at least a portion of the metal oxide chelating groups (e.g., 20-99%, 20-30%, 30-40%, 40-60%, 60-80%, 80-90%, 90-99% (including any range in between)) are bonded to a metal oxide (e.g., metal oxide particles of the present invention).

[0163] Those skilled in the art will understand that there are many options for covalent bonding of chelate moieties (e.g., metal oxide chelate groups) to polymers. For example, an amination chelate moiety may bond to a carboxylated MaSp fiber. Alternatively, a carboxylated chelate moiety may bond to an amination MaSp fiber. Furthermore, an amination chelate moiety may bond to a polymer containing a carboxyl group or a carbonyl group (e.g., PGA). Alternatively, a carboxylated chelate moiety may bond to a polymer containing a hydroxyl group or an amino group (e.g., polylysine or PEI). The inventors have succeeded in synthesizing an amination MaSp fiber bonded to PGA further bonded to a metal oxide chelate group (salicylic acid) as described above.

[0164] In some embodiments, the composite of the present invention comprises a derivatized porous MaSp fiber containing a functional moiety covalently bonded to a metal chelating group. In some embodiments, the metal chelating group is covalently bonded to the functional moiety via a linker as described herein. In some embodiments, the metal chelating group is covalently bonded to the functional moiety via a PGA linker. In some embodiments, each PGA chain is covalently bonded to a plurality of metal chelating groups as described above.

[0165] In some embodiments, the composite of the present invention comprises a derivatized porous MaSp fiber containing a plurality of metal chelating groups bonded thereto, wherein at least a portion of the metal chelating groups (e.g., 20-99%, 20-30%, 30-40%, 40-60%, 60-80%, 80-90%, 90-99% (including any range in between)) are bonded to the metals described herein. In some embodiments, at least a portion of the metal chelating groups are bonded to Pd or a salt thereof (e.g., Pd(acetate)2, PsCl2). In some embodiments, at least a portion of the metal chelating groups are bonded to the metal in its elemental state (e.g., ground state, also called the 0 oxidation state). In some embodiments, at least a portion of the metal chelating groups are bonded to the metal in its oxidation state (e.g., +2). In some embodiments, the metal chelating groups are bonded to at least a partially reduced metal.

[0166] In some embodiments, the composition of the present invention comprises a derivatized fiber of the present invention doped with a metal (a first metal and / or a second metal as described herein), wherein the metal is coordinately bonded to a polymer containing multiple metal chelating groups. In some embodiments, the composition of the present invention comprises Pd complexed with a polyglutaraldehyde containing multiple metal chelating groups (such as IDA), wherein the polyglutaraldehyde is covalently bonded to the derivatized MaSp fiber of the present invention.

[0167] In some embodiments, polymers containing multiple metal chelate groups that form complexes with metals or metal cations are represented as follows: [ka] (In the formula, k is between 10 and 10000, M represents a transition metal (e.g., Pd or a salt thereof), and each m and n independently represents an integer between 0 and 10).

[0168] In another aspect of the present invention, a metal atom (e.g., a first metal) complexed with the polymer of the present invention further bonds with further metal atoms, where the further metal atoms are the same or different atoms. In some embodiments, the metal atom complexed with the polymer of the present invention forms aggregates by further bonding with multiple metal atoms. In some embodiments, the first metal (e.g., Pd) complexed with the polymer of the present invention is uniformly distributed on the outer surface of the derivatized fiber of the present invention. In some embodiments, the first metal (e.g., Pd) forms a metal layer (or first metal layer) on top of the derivatized fiber of the present invention. In some embodiments, the metal layer (e.g., first metal layer and / or second metal layer) has an atomic thickness of 1 to 10 (including any range between them). In some embodiments, the first metal (e.g., Pd) is in colloidal form. In some embodiments, the first metal (e.g., Pd) is in the form of particles ranging from 1 to 500 nm.

[0169] In some embodiments, the first metal, either in the form of fine particles or distinct atoms, forms aggregation centers suitable for bonding the second metal on top of it. In some embodiments, Pd (in its elemental state) complexed with the polymer of the present invention as described herein forms aggregation centers, enabling the deposition of the second metal (e.g., Cu). In some embodiments, the second metal is deposited via electroless plating. In some embodiments, the first metal can facilitate the electroless deposition of the second metal.

[0170] In some embodiments, the second metal (e.g., Cu) is in colloidal form. In some embodiments, the second metal (e.g., Cu) is in the form of particles in the ranges of 1–500 nm, 1–10 nm, 10–50 nm, 50–100 nm, 100–200 nm, and 200–500 nm (including any range in between).

[0171] In some embodiments, the second metal exists either as fine particles or as distinct atoms (the distinct atoms are in an elemental or oxidized state). In some embodiments, the second metal, either in the form of fine particles or distinct atoms, is homogeneously distributed over the derivatized fibers of the present invention. In some embodiments, the first metal and / or the second metal exists as a homogeneous layer over the derivatized fibers of the present invention. In some embodiments, the first metal and / or the second metal exists in an amorphous or crystalline state (e.g., forming substantially crystalline particles). In some embodiments, at least a portion of the first metal and / or the second metal is in a crystalline state.

[0172] "Uniform or homogenous means to describe a distribution of magnitude (or thickness) that varies within a range of less than ±60%, ±50%, ±40%, ±30%, ±20%, or ±10% (including any value in between)."

[0173] In some embodiments, the term “layer” refers to a substantially homogeneous material with substantially uniform thickness. In some embodiments, the shell comprises one or more layers.

[0174] In some embodiments, the derivatized MaSp fiber has a second metal (e.g., Cu) deposited on top of or bonded to the top of a first metal (e.g., Pd) that has been complexed with polyglutaraldehyde covalently bonded to the MaPs fiber. 0 The invention includes a layer of ). In some embodiments, the first metal (e.g., Pd) is chelated or complexed with a metal chelate moiety (e.g., IDA). In some embodiments, the metal chelate moiety is covalently bonded to the polyglutaraldehyde illustrated above herein. The inventors have developed a Cu derivative MaSp fiber containing PGA bonded to an IDA metal chelate group. 0 The doping process was successful.

[0175] In some embodiments, the first metal and / or second metal described herein exist in the form of fine particles or distinct atoms, and the first metal and / or second metal exist independently in an elemental state or an oxidized state.

[0176] In some embodiments, a metal layer (e.g., a first metal layer) in contact with or bonded to the polymer layer forms multiple aggregation sites for a second metal. In some embodiments, the first metal has a high affinity for the coating polymer of the polymer layer. In some embodiments, the first metal is bonded to the coating polymer.

[0177] In some embodiments, the second metal is bonded or aggregated on top of the first metal. In some embodiments, the second metal is in an elemental state. In some embodiments, the second metal is in an oxidized state (e.g., +1 or +2). In some embodiments, the second metal forms a layer on top of the first metal layer. In some embodiments, the second metal has an affinity for the first metal. In some embodiments, the second and first metals are in the form of a layered structure in which each metal layer is separate. In some embodiments, the second and first metals are mixed together in a metal layer to form a single metal layer on top of a polymer layer. In some embodiments, the fibers are at least partially coated by either the first and second metals, or by a combination of the first and second metals.

[0178] In some embodiments, the first metal and optionally the second metal are transition metals as described herein. Transition metals are well known in the art and represent metals containing d-electrons.

[0179] In some embodiments, the first metal has a reduction potential suitable for chemical reduction. In some embodiments, the first and second metals are compatible with electroless deposition. In some embodiments, the first metal can directly reduce the second metal.

[0180] In some embodiments, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, and at least 99% (including any range of these values) of the chelating agent is bound to the metal oxide particles.

[0181] In some embodiments, the w / w ratio of derivatized porous MaSp fibers to metal oxide particles is 0.01:1~100:1, 0.01:1~10:1, 0.01:1~0.05:1, 0.05:1~0.1:1, 0.1:1~0.2:1, 0.2:1~0.3:1, 0.3:1~0.4:1, 0.4:1~0.5:1, 0.5 :1~0.7:1, 0.7:1~0.9:1, 0.5:1~1:1, 0.9:1~1:1, 1:1~1.5:1, 1.5:1~2:1, 2:1~3:1, 3:1~5:1, 5:1~7:1, 7:1~10:1, 10:1~30:1, 30:1~50:1, 50:1~100:1 (including any range in between).

[0182] In some embodiments, the metal oxide particles are characterized by particle sizes of 25-5000 nm, 25-50 nm, 50-100 nm, 100-150 nm, 150-200 nm, 200-300 nm, 300-500 nm, 500-1000 nm, 1000-2000 nm, 2000-3000 nm, 3000-4000 nm, and 4000-5000 nm (including any range in between).

[0183] In some embodiments, the composite is stable for at least 1 month (m), at least 2m, at least 3m, at least 4m, at least 5m, at least 6m, at least 7m, at least 8m, at least 9m, at least 10m, and at least 12m (including any range in between).

[0184] In some embodiments, the metal oxide in the metal oxide particles is in an amorphous state. In some embodiments, the metal oxide in the metal oxide particles is in a crystalline state. In some embodiments, at least a portion of the metal oxide in the metal oxide particles is in an amorphous state.

[0185] In some embodiments, the composites are characterized by high dispersibility in aqueous and / or organic solutions compared to the original metal oxide particles (e.g., lacking MaSp fibers). The composites of the present invention containing titanium oxide with a particle size greater than 300 nm exhibited significantly improved dispersibility in aqueous and / or organic solutions compared to the original titania particles. Aqueous dispersions containing titanium oxide particles bound to salicylate- or PVA-derivativeized MaSp fibers (e.g., exemplary composites of the present invention) showed superior stability compared to control dispersions containing non-derivativeized MaSp fibers. Furthermore, the composites containing titanium oxide particles bound to salicylate-derivativeized MaSp fibers exhibited excellent dispersibility (e.g., able to form stable dispersions), where the w / w ratio of titanium oxide particles to derivatized MaSp fibers is approximately 1:1.

[0186] In some embodiments, the aqueous dispersion formed by the composite of the present invention further comprises a surfactant. Examples of surfactants incorporated for the formation of a stable dispersion include, but are not limited to, TRITON and sodium dodecyl sulfate.

[0187] In some embodiments, the composite is characterized by higher UV irradiation absorption compared to the control. In some embodiments, the control is a derivatized or non-derivatized MaSp fiber lacking metal oxide particles.

[0188] Porous MaSp fibers In some embodiments, the present invention provides a composition comprising derivatized porous MaSp fibers. In some embodiments, the derivatized MaSp fibers are present at a concentration of 0.1% to 90% of the total weight.

[0189] In some embodiments, the porous MaSp fiber comprises at least one MaSp fiber. In some embodiments, the at least one MaSp fiber is present at a concentration of 0.1% to 25%, 0.1% to 20%, 0.1% to 15%, 0.5% to 30%, 1% to 30%, 5% to 30%, or 10% to 30% (including any range in between) of the total weight.

[0190] In some embodiments, the porous MaSp fiber is a MaSp polymer in the form of particles having a size in the range of 0.5 μm to 1.5 μm. In some embodiments, the MaSp fiber is an insoluble polymer. In some embodiments, the porous MaSp fiber has a DSC pattern exhibiting at least one endothermic peak in the range of 200°C to 280°C. In some embodiments, the porous MaSp fiber is characterized by an amide peak in the range of 1615 cm⁻¹ to 1635 cm⁻¹ as measured by FTIR analysis.

[0191] In some embodiments, a composition comprising a MaSp polymer (synthetic MaSp polymer) wherein the MaSp polymer has at least one feature selected from a) an insoluble polymer; b) a particle form having a size in the range of 0.5 μm to 1.5 μm; c) a DSC pattern exhibiting at least one endothermic peak in the range of 200°C to 280°C; and d) an amide peak in the range of 1615 cm⁻¹ to 1635 cm⁻¹ as measured by FTIR analysis.

[0192] In some embodiments, the MaSp fibers have a decomposition temperature (T) of 280°C to 350°C, 290°C to 350°C, 300°C to 350°C, 310°C to 350°C, 320°C to 350°C, 280°C to 330°C, 290°C to 330°C, 300°C to 330°C, 310°C to 330°C, or 320°C to 330°C (including any range in between), as determined by differential scanning calorimetry (DSC). d ) is characterized by each possibility representing a separate embodiment of the present invention.

[0193] In some embodiments, the MaSp fiber has a glass transition temperature (T) of 200°C to 250°C, 210°C to 250°C, 220°C to 250°C, 230°C to 250°C, 200°C to 240°C, 210°C to 240°C, 220°C to 240°C, 230°C to 240°C, 200°C to 230°C, or 210°C to 230°C (including any range in between) as determined by DSC. g ) is characterized by each possibility representing a separate embodiment of the present invention.

[0194] In some embodiments, the MaSp fibers are T-coated at temperatures of 260°C to 320°C, 270°C to 320°C, 280°C to 320°C, 290°C to 320°C, 260°C to 310°C, 270°C to 310°C, 280°C to 310°C, or 290°C to 310°C (including any range in between) as determined by DSC. g This is characterized by the fact that each possibility represents a separate embodiment of the present invention.

[0195] In some embodiments, the MaSp fibers are characterized by a DSC pattern exhibiting at least one endothermic peak in the ranges of 280°C to 350°C, 290°C to 350°C, 300°C to 350°C, 310°C to 350°C, 280°C to 330°C, 290°C to 330°C, 300°C to 330°C, 310°C to 330°C, or 320°C to 330°C (including any range in between), each representing a separate embodiment of the present invention.

[0196] The term “decomposition temperature (T d Where used herein, ) represents the temperature at which decomposition occurs. Thermal decomposition is the process of transformation of extensive chemical species caused by heat.

[0197] Where used herein, the term "glass transition temperature (T)" refers to the glass transition temperature (T) g )" is a substance that is elastic and viscous amorphous liquid (T>T g ) is brittle and glassy amorphous solid (T <T g This represents the temperature at which the transition occurs up to ). This liquid-glass transition (or simply glass transition) is a reversible transition. g ) is generally the melting temperature (T) of the crystalline state of a substance, if present. m It is less than ).

[0198] In some embodiments, porous MaSp fibers are provided, comprising synthetic MaSp polymers in the form of particles. In some embodiments, the particles have sizes ranging from 0.5 μm to 1.5 μm, 0.7 μm to 1.5 μm, 0.8 μm to 1.5 μm, 0.9 μm to 1.5 μm, 0.5 μm to 1 μm, 0.7 μm to 1 μm, 0.8 μm to 1 μm, 0.9 μm to 1 μm, 0.5 μm to 1.3 μm, 0.5 μm to 12 μm, 0.7 μm to 1.3 μm, 0.7 μm to 1.2 μm, or 0.9 μm to 12 μm (including any range in between).

[0199] In some embodiments, the MaSp fiber comprises or consists of an insoluble MaSp polymer. In some embodiments, the insoluble MaSp polymer is in the form of particles. In some embodiments, the insoluble MaSp polymer is insoluble in organic solvents. In some embodiments, the insoluble MaSp polymer is insoluble in aqueous solutions. Where used herein, the terms “MaSp polymer” and “MaSp fiber” are interchangeable herein.

[0200] As used herein, the term “insoluble” refers to a substance that does not dissolve when exposed to an excess of solvent, but can be dispersed to varying degrees. In some embodiments, the term “insoluble” refers to a substance that can dissolve in a solvent at a concentration of less than 10%, less than 5%, less than 2%, or less than 1%. In some embodiments, “insoluble” refers to a substance that can partially dissolve in a solvent at a concentration of less than 0.01% by weight. Solvents according to the present invention include organic solvents and aqueous solutions. In some embodiments, the solvent includes an aqueous surfactant solution. In some embodiments, the solvent includes an aqueous urea solution.

[0201] In some embodiments, MaSp fibers are characterized by a distinct differential scanning calorimetry (DSC) pattern. In some embodiments, “DSC pattern” means representing the location of the peaks. In some embodiments, “peak” means representing the exothermic peak. Throughout this specification, “location of the peak” or “peak position” refers to the peak along the temperature axis in the thermogram pattern, and in some embodiments, it may refer to the location of the peak at any of the peak intensities. Those skilled in the art will understand that the data obtained by DSC measurement depends in part on the equipment used and the environmental conditions (e.g., humidity) at the time the measurement is performed.

[0202] In some embodiments, the MaSp-based polymer is characterized by a DSC pattern exhibiting at least one endothermic peak in the range of 200°C to 280°C. In some embodiments, the disclosed composition is characterized by a DSC pattern exhibiting at least one endothermic peak in the range of 200°C to 270°C, 200°C to 260°C, 200°C to 250°C, 210°C to 280°C, 212°C to 280°C, 215°C to 280°C, 216°C to 280°C, 220°C to 280°C, 210°C to 250°C, 212°C to 250°C, 215°C to 250°C, 216°C to 250°C, 220°C to 250°C, 210°C to 245°C, 210°C to 242°C, or 215°C to 245°C (including any range in between).

[0203] In some embodiments, the MaSp polymer is characterized by a DSC pattern exhibiting at least one endothermic peak at at least 5°C to 100°C, at least 10°C to 100°C, at least 15°C to 100°C, at least 12°C to 100°C, at least 25°C to 100°C, at least 5°C to 80°C, at least 10°C to 80°C, at least 15°C to 80°C, at least 12°C to 80°C, at least 25°C to 80°C, at least 5°C to 50°C, at least 10°C to 50°C, at least 15°C to 50°C, at least 12°C to 50°C, or at least 25°C to 50°C, which is less than the DSC pattern of the corresponding composition containing (MaSp) fibers.

[0204] In some embodiments, the MaSp polymer lacks a DSC peak in the range of about -100°C to about 190°C. In some embodiments, the disclosed compound lacks a DSC peak in the range of about -100°C to about 25°C. In some embodiments, the disclosed composition features at least one DSC pattern lacking an exothermic peak in the range of 40°C to 70°C.

[0205] In some embodiments, the MaSp polymer lacks a DSC peak in the range of about -100°C to about -50°C. In some embodiments, the disclosed compound lacks a DSC peak in the range of about -50°C to about 0°C. In some embodiments, the disclosed compound lacks a DSC peak in the range of about -0°C to about 25°C.

[0206] In some embodiments, the MaSp polymer is characterized by having an amide peak in the range of 1615 cm⁻¹ to 1635 cm⁻¹ as measured by FTIR analysis. In some embodiments, the disclosed composition is characterized by having an amide peak in the range of 1620 cm⁻¹ to 1635 cm⁻¹, 1620 cm⁻¹ to 1630 cm⁻¹, 1621 cm⁻¹ to 1630 cm⁻¹, or 1620 cm⁻¹ to 1625 cm⁻¹ (including any range in between) as measured by FTIR analysis.

[0207] In some embodiments, MaSp-based polymers lack the peak in the 1700 cm⁻¹ to 1800 cm⁻¹ range measured by FTIR analysis.

[0208] In one embodiment, the MaSp polymers of the present invention associate by self-assembly. "Self-assembly" means that monomers, i.e., the synthetic SPIDER SILK proteins of the present invention, spontaneously bind to one another in an energetically favorable manner under normal physiological conditions or at room temperature to form a macromolecular structure having the properties described herein. Furthermore, the MaSp polymers of the present invention are highly elastic and, once assembled, can withstand thorough chemical attack, such as solubilization in a 10% surfactant solution and boiling for at least one hour.

[0209] Tensile strength (or tensile strength) represents the weight a filament can withstand before it breaks. The maximum specific stress that occurs is typically determined by a tensile test of a filament, yarn, or fabric to break the material. In certain embodiments, the MaSp polymers of the present invention have tensile strengths of about 100-3000 MPa (MPa=N / mm2), about 300-3000 MPa, about 500-2700 MPa, about 700-2500 MPa, about 900-2300 MPa, about 1100-2000 MPa, about 1200-1800 MPa, about 1300-1700 MPa, or about 1400-1600 MPa, more specifically about 1500 MPa.

[0210] "Toughness" represents the energy required to fracture a MaSp-based polymer. This is the area under the stress-strain curve, sometimes referred to as "energy to fracture" or "action to break." In certain embodiments, the MaSp-based polymers of the present invention have a toughness of about 20-1000 MJ / m3, about 50-950 MJ / m3, about 100-900 MJ / m3, about 120-850 MJ / m3, about 150-800 MJ / m3, about 180-700 MJ / m3, about 180-750 MJ / m3, about 250-700 MJ / m3, about 280-600 MJ / m3, about 300-580 MJ / m3, about 310-560 MJ / m3, about 320-540 MJ / m3, or about 350-520 MJ / m3, most preferably about 350-520 MJ / m3.

[0211] "Elasticity" describes the property of an object that tends to return to its original size and shape after deformation. Plasticity is deformation that does not recover and is the opposite of elasticity. In the molecular structure of MaSp polymers, recoverable or elastic deformation is made possible by the elongation (rearrangement) of structural bonds between atoms and molecules. Conversely, the fracture and reformation of intermolecular bonds to new stable positions results in irrecoverable or plastic deformation.

[0212] "Extension" refers to an increase in length, expressed as a percentage or proportion of the initial length.

[0213] "Fineness" refers to the average diameter of MaSp-based polymers or filaments (such as biofilaments), usually expressed in microns (micrometers).

[0214] MaSp fiber The terms “MaSp (major ampullate spidroin protein)” and “spidroin protein” are used interchangeably throughout this description and encompass all known MaSp proteins, usually abbreviated as “MaSp” or, in the case of Araneus diadematus, “ADF.” These MaSps are generally of two types, 1 and 2. These terms further include non-native proteins disclosed herein that exhibit a high degree of identity and / or similarity to the repeating regions of at least known MaSp proteins. Further suitable spider silk proteins include MaSp2, MiSp, MiSp2, AcSp, FLYS, FLAS, and flagelliform.

[0215] As used herein, the terms "repeat region", "repeat sequence", or "repeat" refer to recombinant protein sequences derived from repeat units that occur multiple times naturally in spider silk amino acid sequences (e.g., MaSp-1 protein). Those skilled in the art understand that the primary structure of spider silk proteins is considered to consist mainly of a series of small variations of the unit repeat. The unit repeats of naturally occurring proteins often differ from each other. That is, there is little or no exact duplication of unit repeats along the length of the protein. In some embodiments, the synthetic spider silk of the present invention is made such that the primary structure of the protein contains multiple exact repeats of a single unit repeat. In further embodiments, the synthetic spider silk of the present invention contains repeats of a number of one unit repeat, along with a number of second unit repeats. Such a structure is similar to a typical block copolymer. Also, unit repeats of several different sequences can be combined to provide synthetic spider silk with properties suitable for a particular application. The term "direct repeat" as used herein is a repeat in a row (head-to-tail arrangement) where the repeats are similar. In another embodiment, the repeats used to form the synthetic spider silk of the present invention are direct repeats. In some embodiments, the repeats are not found in nature (i.e., they are not naturally occurring amino acid sequences).

[0216] An exemplary sequence containing a repeating sequence is ADF-4:(SEQ ID NO: 1). In some embodiments, the synthetic repeating sequence of the present invention is based on one or more repeating sequences derived from ADF-4(SEQ ID NO: 1) (for example, having high percent identity as defined below herein). As used herein, the term "based on" means a sequence having a high percentage of homology to the repeating sequence.

[0217] In some embodiments, each repeat sequence comprises up to 60 amino acids, up to 55 amino acids, up to 50 amino acids, up to 49 amino acids, up to 48 amino acids, up to 47 amino acids, up to 46 amino acids, up to 45 amino acids, up to 44 amino acids, up to 43 amino acids, up to 42 amino acids, up to 41 amino acids, up to 40 amino acids, up to 39 amino acids, up to 38 amino acids, up to 37 amino acids, up to 36 amino acids, or up to 35 amino acids, the possibilities representing separate embodiments of the invention. In some embodiments, each repeat sequence comprises 5 - 60 amino acids, 10 - 55 amino acids, 15 - 50 amino acids, 20 - 45 amino acids, 25 - 40 amino acids, 25 - 39 amino acids, or 28 - 36 amino acids, the possibilities representing separate embodiments of the invention. In some embodiments, each repeat sequence comprises 30 - 40 amino acids, 31 - 39 amino acids, 32 - 38 amino acids, 33 - 37 amino acids, 34 - 36 amino acids, each possibility representing a separate embodiment of the invention. In further embodiments, each repeat sequence comprises 35 amino acids.

[0218] In some embodiments, the repeat region is independently of Formula 1 0: (X1) Z X2GPGGYGPX3X4X5GPX6GX7GGX8GPGGPGX9X 10 The amino acid sequence shown is (wherein X1 is independently A or G at each position, Z is an integer from 5 - 30, X2 is S or G, X3 is G or E, X4 is G, S, or N, X5 is Q or Y, X6 is G or S, X7 is P or R, X8 is Y or Q, X9 is G or S, and X 10 is S or G). In some embodiments, at least 50% of (X1) Z is A.

[0219] In another embodiment, the repeating region of the MaSP1 protein includes the amino acid sequence described in SEQ ID NO: 2 (SGPGGYGPGSQGPSGPGGYGPGGPGSS). In another embodiment, the repeating region of the MaSP1 protein includes the amino acid sequence described in SEQ ID NO: 3 (AAAAAAAASGPGGYGPGSQGPSGPGGYGPGGPGSS).

[0220] In another embodiment, a repeating region of the MaSP1 protein is provided that shares at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% homology with SEQ ID NO: 1.

[0221] In another embodiment, the homolog shares at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% homology with sequence number 2.

[0222] In another embodiment, the repeating region of the MaSP1 protein has the amino acid sequence described in SEQ ID NO: 1.

[0223] In another embodiment, the MaSP1 protein includes a single N-terminal region selected from the group consisting of SEQ ID NOs: 4 (MSYYHHHHHHDYDIPTTENLYFQGAMDPEFKGLRRRAQLV); SEQ ID NOs: 5 (MSYYHHHHHHDYDIPTTENLYFQGAMDPEFKGLRRRAQLVRPLSNLDNAP); SEQ ID NOs: 6 (MSYYHHHHHHDYDIPTTENLYFQGAMDPEFKGLRRRAQLVDPPGCRNSARAGSS), or any of these functional homologs, variants, derivatives, or fragments. In another embodiment, the C-terminal region homolog shares at least 70% homology with any one of SEQ ID NOs: 4-6.

[0224] In another embodiment, the MaSP1 protein further comprises a single C-terminal region selected from the group consisting of functional homologs, variants, derivatives, fragments, or variants of SEQ ID NO: 7 (VAASRLSSPAASSRVSSAVSSLVSSGPTNGAAVSGALNSLVSQISASNPGLSGCDALVQALLELVSALVAILSSASIGQVNVSSVSQSTQMISQALS); SEQ ID NO: 8 (GPSGPGAYGPSPSASASVAASRLSSPAASSRVSSAVSSLVSSGPTNGAAVSGALNSLVSQISASNPGLSGCDALVQALLELVSALVAILSSASIGQVNVSSVSQSTQMISQALS); or any of these. In another embodiment, the homolog of the N-terminal region shares at least 70% homology with SEQ ID NOs: 7-8.

[0225] In some embodiments, the MaSp fiber comprises a mixture of proteins disclosed in International Patent Publication No. 2017025964.

[0226] In some embodiments, the MaSp fiber contains a mutant protein obtained by expressing the mutant nucleic acid sequence.

[0227] In some embodiments, the MaSp1 protein further comprises at least one tag sequence. Non-limiting examples of tags that may be used in the present invention include His tags, HA tags, T7 tags, and the like. Those skilled in the art are well aware of other suitable tags or other fusion partners.

[0228] When used herein, “amino acid” refers to naturally occurring and synthetic amino acids, as well as amino acid analogs and amino acid mimetics that function in a similar manner to naturally occurring amino acids. Naturally occurring amino acids are those encoded by the genetic code and those that are later modified, such as hydroxyproline, γ-carboxyglutamate, and O-phosphoserine. “Amino acid analog” refers to compounds that have the same basic chemical structure as naturally occurring amino acids, i.e., hydrogen, a carboxyl group, an amino group, and an α-carbon bonded to an R group, such as homoserine, norleucine, methionine sulfoxide, and methionine methylsulfonium. Such analogs have a modified R group or a modified peptide skeleton but retain the same basic chemical structure as naturally occurring amino acids. “Amino acid mimetic” refers to chemical compounds that have a structure different from the general chemical structure of an amino acid but function in a similar manner to a naturally occurring amino acid. Amino acids may be represented herein by commonly known three-letter or one-letter symbols as recommended by the IUPAC-IUB Biochemical Nomenclature Commission.

[0229] An "amino acid sequence" or "peptide sequence" describes the order in which amino acid residues linked by peptide bonds are located in a chain of peptides and proteins. This sequence is generally recorded from the N-terminus, which contains a free amino group, to the C-terminus, which contains a free carboxyl group. Although an amino acid sequence is often called a peptide or protein sequence when it represents the primary structure of a protein, a distinction should be made between the terms "amino acid sequence" or "peptide sequence" and "protein." This is because proteins are defined as amino acid sequences that have folded into a specific three-dimensional structure and have undergone post-translational modifications such as phosphorylation, acetylation, glycosylation, sulfhydryl bond formation, and cleavage.

[0230] Where used herein, “isolated” or “substantially purified” means, in the context of the synthetic spider silk amino acid sequences or nucleic acid molecules encoding such sequences as illustrated by the present invention, that the amino acid sequences or polynucleotides have been removed from their natural state or have been modified from their natural state. “Isolated” does not necessarily reflect the degree to which the amino acid sequences or nucleic acid molecules are purified. However, it should be understood that such molecules, purified to a certain degree, are “isolated.” If a molecule does not present in its natural state, i.e., does not exist naturally, then that molecule is “isolated,” whether it exists or not. For example, an amino acid sequence or polynucleotide that does not exist naturally in humans is “isolated,” even if it does exist in humans.

[0231] The terms “isolated” or “substantially purified,” when applied to amino acid sequences or nucleic acids, mean that the amino acid sequence or nucleic acid essentially does not contain other cellular components to which it is bound in its native state. This can be in a homogeneous state, or it can be dry or in aqueous solution. Purity and homogeneity are usually determined using analytical chemistry techniques such as polyacrylamide gel electrophoresis or high-performance liquid chromatography. The amino acid sequence or nucleic acid that is the dominant species present in the formulation is substantially purified.

[0232] In some embodiments, the repeat is a repeat of a homolog, variant, derivative, or fragment thereof of the repeat region of the MaSp1 protein. In some embodiments, the repeat is a repeat of a homolog, variant, derivative, or fragment thereof of the repeat region of the ADF-4 protein.

[0233] As used herein, the term “functional,” as in “functional homolog, variant, derivative, or fragment,” refers to an amino acid sequence having a biological function or activity identified through a defined functional assay. More specifically, a defined functional assay is the formation of self-assembling fibers in cells expressing a functional homolog, variant, derivative, or fragment.

[0234] An amino acid sequence or nucleic acid sequence is a homolog of the corresponding amino acid sequence or nucleic acid if it is determined that the homology is at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 92%, at least 94%, at least 96%, at least 98%, or at least 99%.

[0235] Homology, as used herein, can be determined based on the percentage identity between two amino acids (peptides) or DNA sequences. Generally, the two sequences being compared are aligned to provide the greatest correlation between them. The alignment of the two sequences is tested to determine the number of positions that provide a precise amino acid (or nucleotide) correspondence between the two sequences, and this number is divided by the total length of the alignment and multiplied by 100 to provide a percentage identity figure. This percentage identity figure is particularly suitable for sequences of the same or very similar lengths and may be determined over the full length of the sequences being compared if they exhibit significant homology, or it may be determined over a shorter defined length, which is more suitable for sequences of unique lengths or has a lower level of homology. Methods for comparing the identity of two or more sequences are well known in the art. Therefore, programs available in the Wisconsin Sequence Analysis Package, version 9.1, such as GAP and BESTFIT, can be used to determine percentage identity between two amino acid sequences and percentage identity between two polynucleotide sequences. BESTFIT uses Smith and Waterm's "local homology" algorithm to find the best single region of similarity between two sequences. BESTFIT is more suitable for comparing two polypeptide sequences or two polynucleotide sequences that are not similar in length, as the program assumes that the shorter sequence represents part of the longer sequence. For comparison, GAP aligns the two sequences and finds the "maximum similarity" using Needleman and Wunsch's algorithm. GAP is more suitable for comparing sequences of approximately the same length, as the alignment is predicted over the entire length. Preferably, the parameters "Gap Weight" and "Length Weight" used in each program are 50 and 3 for polynucleotide sequences and 12 and 4 for polypeptide sequences, respectively. Preferably, percentage identity and similarity are determined when the two sequences being compared are optimally aligned.

[0236] The terms "identical," "substantial identity," "substantial homology," or percent "identity" in the context of two or more amino acid or nucleic acid sequences refer to two or more sequences or subsequences that, when compared and aligned with respect to the maximum correspondence over a comparison window or specified region, measured using the BLAST or BLAST 2.0 sequence comparison algorithms with the default parameters described below, or by manual alignment and visual inspection, are the same as a specified region (e.g., amino acid sequence SEQ ID NO: 2 or 3) or have amino acid residues or nucleotides that are the same for a specified percentage (i.e., about 60% identity, or at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or 99% identity). Thus, such sequences are "substantially identical." This definition can also apply to or represent the complement of a test sequence. This definition also includes sequences with deletions and / or additions, as well as sequences with substitutions. Preferred algorithms can account for gaps, etc.

[0237] In sequence comparison, usually, one sequence acts as a reference sequence against which a test sequence is compared. When using a sequence comparison algorithm, the test sequence and the reference sequence are entered into a computer, and if necessary, the coordinates of subsequences are specified and the program parameters of the sequence algorithm are specified. Preferably, the default program parameters can be used or alternative parameters can be specified. Thus, the sequence comparison algorithm calculates the percent sequence identity of the test sequence compared to the reference sequence based on the program parameters.

[0238] The present invention further encompasses amino acid sequences comprising 2 to 70 repeats of any one variant of SEQ ID NO: 1, 2, or 3. Where used herein, the terms “variant” or “substantially similar” include amino acid or nucleotide sequences that differ from a specifically identified sequence in which one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, or 25) amino acid residues or nucleotides are deleted, substituted, or added. A variant may be a naturally occurring allele variant or a variant of non-natural origin. A variant or substantially similar sequence represents an amino acid sequence or nucleic acid fragment that may be characterized by a percentage of identity between those amino acid or nucleotide sequences and the amino acid or nucleotide sequences described herein, as determined by a common algorithm used in the most modern context. Preferred amino acid or nucleic acid fragments are fragments having an amino acid or nucleotide sequence having at least about 40 or 45% sequence identity, preferably about 50 or 55% sequence identity, more preferably about 60 or 65% sequence identity, more preferably about 70 or 75% sequence identity, more preferably about 80 or 85% sequence identity, and even more preferably about 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% sequence identity when compared to a reference sequence.

[0239] In one embodiment, the MaSp polymer is a fiber.

[0240] In one embodiment, the MaSp polymer is composed of monomers. In one embodiment, multiple monomers are arranged in nanofibers. In one embodiment, multiple nanofibers are arranged in or constitute a fiber. In one embodiment, the monomers or nanofibers in the MaSp polymer or fiber have a diameter of 4 to 16 nm. In one embodiment, the monomers or nanofibers in the MaSp polymer or fiber have a diameter of 6 to 14 nm. In one embodiment, the monomers or nanofibers in the MaSp polymer or fiber have a diameter of 8 to 12 nm. In one embodiment, the fiber or MaSp polymer has a diameter of 70 to 450 nm. In one embodiment, the protein fiber or MaSp polymer has a diameter of 80 to 350 nm. In one embodiment, the fiber or MaSp polymer has a diameter of 80 to 300 nm. In one embodiment, the fiber or MaSp polymer has a diameter of 150 to 250 nm. In one embodiment, the fiber or MaSp polymer is arranged as a coil. In one embodiment, a single fiber or one MaSp-based polymer is arranged as a coil. In one embodiment, the coil has a diameter of 5 to 800 micrometers. In one embodiment, the coil has a diameter of 5 to 500 micrometers. In one embodiment, the coil has a diameter of 5 to 30 micrometers. In one embodiment, the coil has a diameter of 5 to 20 micrometers. In one embodiment, the fiber or MaSp-based polymer has a length of 5 to 800 micrometers. In one embodiment, the fiber or MaSp-based polymer has a length of 30 to 300 micrometers.

[0241] In one embodiment, the fiber or MaSp polymer is branched. In one embodiment, the fiber or MaSp polymer contains 1 to 10 branches. In one embodiment, the fiber or MaSp polymer is carbohydrate-free. In one embodiment, the fiber or MaSp polymer is not glycosylated. In one embodiment, the fiber or MaSp polymer is fat or fatty acid-free. In one embodiment, the fiber or MaSp polymer is phosphorus-free. In one embodiment, the fiber or MaSp polymer is free of further non-MaSp proteins. In one embodiment, the fiber or MaSp polymer is free of further polymers (e.g., synthetic polymers, non-MaSp peptides, non-MaSp proteins). In one embodiment, the fiber or MaSp polymer is substantially free of further polymers; in one embodiment, "free of" means "lacking" or essentially "lacking".

[0242] In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:10. In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:10 to 1:1500. In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:50 to 1:1000. In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:100 to 1:1200. In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:100 to 1:1000. In one embodiment, the aspect ratio of the length of the fiber or MaSp polymer to its diameter is at least 1:500 to 1:1000.

[0243] When used herein, the terms derivative and functional derivative refer to the amino acid sequence of the present invention, including any insertion, deletion, substitution, and modification.

[0244] It should be understood that the term “insertion,” as used herein, means the addition of any of the amino acid residues to the sequence of the present invention, specifically 1 to 50 amino acid residues, more specifically 20 to 1 amino acid residues, more specifically 1 to 10 amino acid residues, and most specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 amino acid residues. Furthermore, the amino acid sequence of the present invention may be extended at its N-terminus and / or C-terminus with a variety of identical or different amino acid residues.

[0245] Amino acid "substitution" is the result of replacing one amino acid with another amino acid that has a similar structure and / or chemical properties, i.e., the substitution of a conserved amino acid. Amino acid substitutions can be made based on the similarity of the polarity, charge, solubility, hydrophobicity, hydrophilicity, and / or amphiphilicity of the residues involved. For example, nonpolar (hydrophobic) amino acids include alanine, leucine, isoleucine, valine, proline, phenylalanine, tryptophan, and methionine; polar neutral amino acids include glycine, serine, threonine, cysteine, tyrosine, asparagine, and glutamine; positively charged (basic) amino acids include arginine, lysine, and histidine; and negatively charged (acidic) amino acids include aspartic acid and glutamic acid.

[0246] In another embodiment, the repeat sequence of the present invention has 17 or fewer amino acid substitutions for any one sequence of SEQ ID NO: 2 or 3, which is 16 or fewer, 15 or fewer, 14 or fewer, 13 or fewer, 12 or fewer, 11 or fewer, 10 or fewer, 9 or fewer, 8 or fewer, or 7 or fewer. In one embodiment, the repeat sequence of the present invention has at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, or at least 13 amino acid substitutions for any one sequence of SEQ ID NO: 2 or 3.

[0247] With respect to amino acid sequences, those skilled in the art recognize that individual substitutions, deletions, or additions to the sequences of amino acids, nucleic acids, peptides, polypeptides, or proteins, which modify, add, or delete a single amino acid or a small number of amino acids in the encoded sequence, are conservedly modified variants (where the modification results in the substitution of an amino acid with a chemically similar amino acid). Tables of conservative substitutions that provide functionally similar amino acids are well known in the art. Such conservedly modified variants are added to, and not excluded from, the polymorphic variants, interspecies homologs, and alleles of the present invention.

[0248] For example, substitutions can occur in which an aliphatic amino acid (G, A, I, L, or V) is replaced by another member of the group, or by the substitution of one polar residue with another residue, such as arginine being replaced by lysine, glutamic acid by aspartic acid, or glutamine by asparagine. The following eight groups each contain other exemplary amino acids that are conserved substitutions with each other: 1) alanine (A), glycine (G); 2) aspartic acid (D), glutamic acid (E); 3) asparagine (N), glutamine (Q); 4) arginine (R), lysine (K); 5) isoleucine (I), leucine (L), methionine (M), valine (V); 6) phenylalanine (F), tyrosine (Y), tryptophan (W); 7) serine (S), threonine (T); and 8) cysteine ​​(C), methionine (M).

[0249] A conservative nucleic acid substitution is a nucleic acid substitution that results in a conservative amino acid substitution as defined above.

[0250] The amino acid sequence variants of the present invention are repeat units represented by either SEQ ID NO: 2 or 3, and may have at least 80% sequence similarity, at least 85% sequence similarity, 90% sequence similarity, or at least 95%, 96%, 97%, 98%, or 99% sequence similarity at the amino acid level.

[0251] The amino acid sequence of the present invention may comprise 2 to 70 repeats of SEQ ID NO: 1 or SEQ ID NO: 3, or fragments thereof. A “fragment” constitutes an amino acid or fraction of a DNA sequence in a specific region. A peptide sequence fragment is at least one amino acid shorter than the specific region, and a DNA fragment is at least one base pair shorter than the specific region. A fragment may be truncated at the C-terminus, N-terminus, or both. An amino acid fragment may comprise at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, at least 16, at least 17, at least 18, at least 19, at least 20, at least 21, at least 22, at least 23, at least 24, at least 24, at least 26, at least 27, at least 28, at least 29, at least 30, at least 31, at least 32, at least 33, or at least 34 amino acids of SEQ ID NO: 1 or 3.

[0252] The amino acid sequence variants of the present invention are characterized by the exchange of one or more (point mutations), up to a maximum of 10, amino acids for one or more other amino acids. These are the result of corresponding mutations at the DNA level that lead to different combinations.

[0253] Furthermore, the present invention relates to derivatives of the amino acid sequence of the present invention. Derivatives of the amino acid sequence of the present invention are obtained by derivatizing, for example, a functional group such as an amino, hydroxyl, mercapto, or carboxyl group, which is then glycosylated, acylated, amidated, or esterified. In glycosylated derivatives, the oligosaccharide is typically bonded to asparagine, serine, threonine, and / or lysine. Acylated derivatives are particularly acylated with naturally occurring organic or inorganic acids, such as acetic acid, phosphoric acid, or sulfuric acid, which usually occurs at the N-terminal amino or hydroxyl group, particularly tyrosine or serine, respectively. Esters are esters of naturally occurring alcohols, such as methanol or ethanol. Further derivatives are ammonium salts formed with salts, particularly pharmaceutically acceptable salts, such as metal salts, such as alkali metal salts and alkaline earth metal salts, such as salts of sodium, potassium, magnesium, calcium, or zinc, or with ammonia or suitable organic amines, such as lower alkylamines, such as triethylamine, or hydroxy lower alkylamines, such as 2-hydroxyethylamine.

[0254] In some embodiments, the silk protein of the present invention lacks post-translational modifications.

[0255] In some embodiments, the silk proteins of the present invention are biodegradable. This feature can be important in the pharmaceutical field, for example, whenever the silk protein is intended for in vivo use where biological degradation is desirable. This feature may find applications, in particular, in suture materials and wound closure and covering systems.

[0256] In some embodiments, the MaSp fibers of the present invention are produced using an expression vector containing a suitable nucleic acid sequence, the nucleic acid sequence being under the control of expression of a operably bound promoter and optionally a control sequence. An exemplary expression system, for example, is known in the art in International Patent Publication No. 2020 / 050752.

[0257] In some embodiments, MaSp proteins result in a defined structure formed by self-assembly. In some embodiments, MaSp proteins exist in a network form. In some embodiments, MaSp proteins exist in a complex form. In some embodiments, MaSp proteins induce a defined secondary structure, such as a β-turn, γ-turn, β-sheet, or α-helix.

[0258] In some embodiments, the MaSp proteins or MaSp polymers used interchangeably herein are in the form of fibers. “Fiber,” as used herein, means a fine strand of fibrous material composed of two or more filaments twisted together. “Filament” means an elongated, thread-like object or structure of indeterminate length ranging from a minute to more than one mile. Specifically, synthetic spider silk filaments are minute and proteinaceous. “Biofilament” means a filament made from a protein containing spider silk protein produced by recombinant technology. In some embodiments, the term “fiber” does not include unsystematized aggregates or precipitates.

[0259] In some embodiments, protein fibers are characterized by a size in at least one dimension (e.g., diameter, length). For example, but not limited to, fiber diameters are 10 nm to 1 μm, 20 to 100 nm, and 10 to 50 nm.

[0260] In some embodiments, the fibers are composed of nanofibers. In some embodiments, the nanofibers have diameters of, for example, 1 nm, about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm, about 15 nm, about 16 nm, about 17 nm, about 18 nm, about 19 nm, about 20 nm, about 21 nm, about 22 nm, about 23 nm, about 24 nm, about 25 nm, about 26 nm, about 27 nm, about 28 nm, about 29 nm, about 30 nm, about 31 nm, about 32 nm, about 33 nm, about 34 nm, about 35 nm, about 36 nm, about 37 nm, about 38 nm, about 40 nm, about 42 nm, about 44 nm, about 46 nm, about 48 nm, or about 50 nm (including any value or range between them). In one embodiment, the nanofibers have a diameter of 3 to 7 nm. In another embodiment, the nanofibers have a diameter of 4 to 6 nm.

[0261] In some embodiments, the length of the disclosed fibers is 1–200 μm, 10–100 μm, 100–500 μm, or 200–500 μm.

[0262] In some embodiments of any one of the embodiments described herein, the disclosed fibers (e.g., particles) are characterized by a porous structure. In some embodiments, the porous structure is characterized by a porosity of at least 30% (e.g., 30-99%). In some embodiments, the porous structure is characterized by a porosity of at least 50% (e.g., 50-99%). In some embodiments, the porous structure is characterized by a porosity of at least 60% (e.g., 60-99%). In some embodiments, the porous structure is characterized by a porosity of at least 70% (e.g., 70-99%). In some embodiments, the porous structure is characterized by a porosity of at least 80% (e.g., 80-99%). In some embodiments, the porous structure is characterized by a porosity of at least 90% (e.g., 90-99%). In some embodiments, the porous structure is characterized by a porosity of about 90%.

[0263] In this specification, the term “porosity” refers to the percentage of volume of a material consisting of voids (e.g., a “sponge-like” material). In another embodiment, porosity is measured by the amount of voids or lumens within the surface area divided by the total surface area (porous and non-porous).

[0264] In some embodiments, the porous structure of the disclosed fibers allows for efficient water absorption at the fiber surface. That is, although we do not wish to be bound by any particular theory, this remarkable finding can be explained in terms of the structure of the disclosed fibers and their porosity, which are distinctly different from native spider silk found in nature.

[0265] In any one of the embodiments described herein, the disclosed fibers are characterized by having an average diameter of nanoscale size.

[0266] In some embodiments, the disclosed fibers are characterized by having an average diameter in the range of 1 to 50 nm. In some such embodiments, the average diameter is in the range of 3 to 50 nm. In some such embodiments, the average diameter is in the range of 5 to 50 nm. In some such embodiments, the average diameter is in the range of 1 to 40 nm. In some such embodiments, the average diameter is in the range of 1 to 30 nm. In some such embodiments, the average diameter is in the range of 5 to 40 nm.

[0267] In some embodiments, the MaSp fibers include a plurality of pores. In some embodiments, the porous MaSp fibers include a plurality of small fibers (e.g., nanofibers) as illustrated below herein (Figures 19A and 19B). In some embodiments, the MaSp fibers are in the form of particles as described later herein. In some embodiments, the MaSp fibers are as described later herein. In some embodiments, the composition includes a plurality of MaSp fibers. In some embodiments, the plurality of MaSp fibers include fibers having different chemical compositions and / or different molecular weights (MW).

[0268] As will be further illustrated in the following sections of examples, in some embodiments, the multiple disclosed fibers may be in the form of a self-assembled structure or matrix. In some embodiments, this matrix may be suitable for a biomaterial.

[0269] In some embodiments, this matrix is ​​suitable for cell proliferation and maintaining or promoting cell activity, as further described below herein.

[0270] In some embodiments, the term “self-assembled” refers to a structure resulting from a self-assembly process (e.g., a spontaneous self-assembly process) based on a series of bonding chemical reactions between at least two domains of a fiber, which occurs when bonding groups on one domain are close enough and oriented to allow structural bonding with another domain. In other words, bonding interactions result in encounters that lead to the bonding of domains of a fiber (including multiple fibers) to each other. In some embodiments, the bonded domains are not parallel to each other. Furthermore, arrangements are considered in which there are more than two domains of the self-assembled structure, each engaging in a different plane.

[0271] Notably, in some embodiments, the density of the self-assembled fibers (e.g., about 80% voids) is 0.1 g / cm³. 3 ~0.4g / cm 3 , or 0.2 g / cm³ 3 ~0.3g / cm 3 It falls within this range. In exemplary embodiments, the density of self-assembled fibers is approximately 0.26 g / cm³. 3 That is the case.

[0272] Surface hydration testing with nanoscale spatial and temporal resolution is a field that has emerged from both theoretical and practical aspects.

[0273] As shown in the Examples section below, the disclosed fibers exhibited a high degree of surface hydration, demonstrating remarkable fluid absorption properties relative to their volume and weight.

[0274] In some embodiments, the polymer is hydrophobic. In some embodiments, the polymer is UV-cured.

[0275] In some embodiments, the disclosed complex is biostable. In some embodiments, the disclosed complex is biocleavable. In some embodiments, the disclosed complex is biodegradable.

[0276] In some embodiments, the term “biostable” refers to a compound or polymer that maintains its intactness under physiological conditions (e.g., does not decompose in vivo and is therefore not biodegradable or biologically cleavable).

[0277] In some embodiments, "biodegradable" refers to a substance that can be broken down into degradation products under physiological and / or environmental conditions. Such physiological and / or environmental conditions include, for example, hydrolysis (degradation via hydrolytic cleavage), enzymatic catalysis (degradation by enzymes), and mechanical interactions. The term typically refers to a substance that degrades under these conditions such that 50% by weight of the substance degrades within a period of less than one year.

[0278] In some embodiments, the term “biodegradable” also encompasses the term “bioresorbable,” which, when used in the context of embodiments of the present invention, refers to a substance that decomposes under physiological conditions and undergoes bioresorption into the host organism, i.e., breaks down products that become metabolites of the host organism’s biochemical system.

[0279] Medicated cosmetic composition In another embodiment, there is a medicated cosmetic composition comprising an effective amount of the composition and / or complex of the present invention and a cosmetically acceptable carrier. In some embodiments, the composition and / or complex of the present invention is in the form of a cosmetic active ingredient. In some embodiments, the medicated cosmetic composition comprises a cosmetic active ingredient and a cosmetically acceptable carrier, the cosmetic active ingredient comprising the composition and / or complex of the present invention.

[0280] In some embodiments, the weight / weight (w / w) concentration of the composition and / or composite of the present invention in the composition is 1 to 95%.

[0281] In some embodiments, the w / w concentration of the composition and / or complex of the present invention in the medicinal cosmetic composition is 1-5%, 5-10%, 10-15%, 15-20%, 20-30%, 30-35%, 35-40%, 40-45%, 45-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-80%, 80-90%, 90-95% (including any range or value between these).

[0282] In some embodiments, the w / w concentration of the cosmetic active ingredient in the medicated cosmetic composition is 1-5%, 5-10%, 10-15%, 15-20%, 20-30%, 30-35%, 35-40%, 40-45%, 45-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-80%, 80-90%, 90-95% (including any range or value between these).

[0283] In some embodiments, the cosmetic active ingredient is encapsulated or incorporated within a twisted structure of derivatized MaSp fibers (hereinafter referred to as the “matrix”). In some embodiments, the cosmetic active ingredient is embedded within the matrix.

[0284] In some embodiments, the cosmetically acceptable carrier concentration in the medicinal cosmetic composition is 60-95(w / w)%, 60-70(w / w)%, 70-75(w / w)%, 75-80(w / w)%, 80-85(w / w)%, 85-90(w / w)%, 90-92(w / w)%, 92-95(w / w)%, or 95-97(w / w)% (including any range or value between these). In some embodiments, the terms “cosmetically acceptable carrier” and “carrier” are used interchangeably herein.

[0285] In some embodiments, the carrier is a physiologically suitable carrier. Exemplary physiologically suitable carriers are listed below herein, and further physiologically suitable carriers are well known in the art.

[0286] In some embodiments, the carrier contains an emulsifier, which can reduce interfacial tension between phases and improve the formulation and stability of the emulsion. The emulsifier can be nonionic, cationic, anionic, or amphoteric (see McCutcheon's (1986); U.S. Patents No. 5,011,681; No. 4,421,769; No. 3,755,560).

[0287] Non-limiting examples of emulsifiers include glycerin esters, propylene glycol esters, polyethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, sorbitol esters, sorbitan anhydride esters, carboxylic acid copolymers, glucose esters and ethers, ethoxylated ethers, ethoxylated alcohols, alkyl phosphates, polyoxyethylene fatty acid ether phosphates, fatty acid amides, acyl lactates, soaps, TEA stearate, DEA oleth-3 phosphate, polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soy sterol (soy sterol), steareth-2, steareth-20, steareth-21, ceteareth-20, and PPG-2. Examples include methyl glucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetyl phosphate, cetyl ethanolamine, polysorbate 60, glyceryl stearate, PEG-100 stearate, or any combination thereof.

[0288] In some embodiments, the w / w ratio of the cosmetic active ingredient in the medicated cosmetic composition to the carrier is up to 100:1, up to 80:1, up to 60:1, up to 50:1, up to 40:1, up to 30:1, up to 20:1, up to 10:1, up to 9:1, up to 8:1, up to 7:1, up to 6:1, up to 5:1, up to 4:1, up to 3:1, up to 2:1, and up to 1:1 (including any range in between).

[0289] In some embodiments, the medicated cosmetic composition of the present invention is a solid composition. In some embodiments, the medicated cosmetic composition of the present invention is in the form of pellets or powder. In some embodiments, the medicated cosmetic composition of the present invention is in the form of a film. In some embodiments, the medicated cosmetic composition of the present invention is in the form of a semi-solid (e.g., a gel or hydrogel). In some embodiments, the medicated cosmetic composition of the present invention is substantially homogeneous. In some embodiments, the cosmetic active ingredients and carriers are homogeneously mixed in the composition.

[0290] In some embodiments, the medicinal cosmetic composition (e.g., a solid composition) substantially lacks at least one of a solvent, a surfactant, a carrier, particles, or a combination thereof, where substantially at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of the composition.

[0291] In some embodiments, the medicinal cosmetic composition of the present invention further comprises 0.1% to 95% of a solvent, a film-forming agent, a pigment, a dye, a stabilizer, an oil, and a thickener, or a combination thereof.

[0292] In some embodiments, the medicinal cosmetic composition of the present invention further comprises a solvent. In some embodiments, the w / w content of the solvent in the composition is 10-90%, 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range or value between these).

[0293] In some embodiments, the solvent is aqueous or organic solvent. In some embodiments, the organic solvent is as described herein.

[0294] In some embodiments, the medicinal cosmetic composition of the present invention is a liquid or semi-liquid composition. In some embodiments, the liquid or semi-liquid composition is characterized by a viscosity of 50-3000 cP, 50-100 cP, 100-300 cP, 300-500 cP, 500-1000 cP, 1000-2000 cP, or 2000-3000 cP (including any range in between) at 25°C.

[0295] In some embodiments, the medicinal cosmetic composition of the present invention (e.g., a liquid composition) is selected from liquids, dispersants, emulsions, gels, hydrogels, semi-liquids, and foams, or combinations thereof. In some embodiments, the composition (e.g., a liquid composition) is substantially devoid of solvents, surfactants, carriers, particles, or combinations thereof, wherein substantially the composition comprises at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, and at least 99% by weight (including any range or value between these).

[0296] In some embodiments, the medicinal cosmetic composition (e.g., a liquid composition) of the present invention further comprises a thickening agent. In some embodiments, the w / w content of the thickening agent in the composition is 1-20%, 1-2%, 2-5%, 5-7%, 4-6%, 6-8%, 8-10%, 10-12%, 12-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range or value between these). In some embodiments, the thickening agent provides the liquid composition with a predetermined viscosity.

[0297] Non-limiting examples of thickeners include, but are not limited to, stearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenyl alcohol, palmitic acid, PEG, polyvinylpyrrolidone, polyacrylates, or derivatives thereof (such as esters, crosslinked polyacrylates, or combinations thereof), polyacrylamides (e.g., multiblock copolymers of acrylamide and acrylic acid and acrylamide substituted with substituted acrylic acid or combinations thereof), and gums (e.g., cellulose, carboxymethyl, hydroxyethylcellulose, cellulose propionate carboxylate, hydroxyethylcellulose, crystalline cellulose, sodium cellulose sulfate, amylopectin, carrageenan, dextrin, guar gum, guar hydroxypropyltrimonium chloride, hydroxypropyl chitosan, kelp, locust bean gum, natto gum, tragacanth gum, xanthan gum, acacia, and agar, or combinations thereof), or combinations thereof.

[0298] In some embodiments, the medicinal cosmetic composition further comprises additives. In some embodiments, the additives include antimicrobial agents (e.g., methylparaben, propylparaben, butylparaben, ethylparaben, isobutylparaben, etc.) and skin conditioning agents (e.g., aloe extract, allantoin, bisabolol, ceramide, dimethicone, and dipotassium glycyrrhizate).

[0299] In some embodiments, the medicated cosmetic composition is a cosmetic formulation. In some embodiments, the cosmetic formulation contains ingredients suitable for use in cosmetic products.

[0300] In some embodiments, the compositions and / or complexes of the present invention are substantially stable in the medicinal cosmetic composition.

[0301] In some embodiments, the medicated cosmetic composition is biocompatible. In some embodiments, the medicated cosmetic composition enhances the bioaccessibility of hydrophobic or hydrophilic cosmetic active ingredients. In some embodiments, the medicated cosmetic composition enhances the bioaccessibility of a compound, which is a cosmetic active ingredient selected from polysaccharides, α-hydroxycarboxylic acids, hydrating agents, etc. (as illustrated herein). The term “bioaccessibility,” as used herein, refers to the property of any one of the compositions of the present invention to release a cosmetic active ingredient in vitro. In vitro release can be evaluated using a skin tape test (described in the Examples section).

[0302] In some embodiments, the medicated cosmetic composition increases the bioavailability and / or bioaccessibility of the cosmetic active ingredients. In some embodiments, the derivatized MaSp-based fibers substantially reduce the degradation of the cosmetic active ingredients embedded within them.

[0303] In some embodiments, the medicinal cosmetic composition of the present invention is in the form of a cosmetic. In some embodiments, the medicinal cosmetic composition of the present invention is in the form of a composition that can be diffused locally, a sprayable composition, an aerosolized composition, an injectable composition, an edible composition, a tablet, a gel capsule, or a pill.

[0304] In some embodiments, the medicinal cosmetic composition is a sunscreen composition comprising an effective amount (e.g., a cosmetically effective amount) of the complex of the present invention. In some embodiments, the sunscreen composition comprises an effective amount of a derivatized MaSp fiber comprising a functional moiety covalently bonded to a metal oxide chelate group, wherein the functional moiety and the metal oxide chelate group are as described herein, and the derivatized MaSp fiber comprises any MaSp fiber (e.g., porous and / or non-porous MaSp fiber) covalently bonded to a metal oxide chelate group as described herein.

[0305] In some embodiments, the sunscreen composition is intended to absorb at least a portion of UV radiation. In some embodiments, the sunscreen composition is intended to reduce UV exposure to the skin in question.

[0306] In some embodiments, the reduction in UV exposure is at least 20%, at least 30%, at least 50%, at least 70%, at least 90%, at least 95%, or at least 99% (including any range in between).

[0307] In some embodiments, the medicated cosmetic composition of the present invention is characterized as a sunscreen composition having a sunscreen index (SPF) of 1 to 100.

[0308] In some embodiments, the sunscreen composition of the present invention is characterized by a sunscreen index (SPF) of 1-100, 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-100 (including any range in between).

[0309] In some embodiments, the effective amount includes an amount of the complex sufficient to obtain a reduction in UV exposure, the reduction being as described herein. In some embodiments, the effective amount includes a w / w concentration of the complex in the sunscreen composition in the ranges of 0.01-95%, 0.01-0.1%, 0.1-0.5%, 0.5-0.1%, 0.1-0.5%, 0.5-1%, 1-5%, 5-10%, 10-20%, 20-30%, 30-50%, 50-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0310] In some embodiments, the medicinal cosmetic composition is a hair color composition comprising an effective amount (e.g., a cosmetically effective amount) of the derivatized porous MaSp fibers of the present invention bound to a dye and / or pigment. In some embodiments, the hair color composition comprises an effective amount of derivatized MaSp fibers bound to a dye and / or pigment, wherein the derivatized MaSp fibers comprise any MaSp fibers (e.g., porous and / or non-porous MaSp fibers) covalently bonded to a functional group (e.g., a positively or negatively charged group) as described herein. In some embodiments, the effective amount comprises an amount of a complex (e.g., the derivatized porous MaSp fibers of the present invention bound to a dye and / or pigment) sufficient to stably bond to the hair in question and color the hair in question, for example, to obtain hair color.

[0311] In some embodiments, the dye and / or pigment are bonded to the derivatized MaSp fibers (e.g., porous or non-porous MaSp fibers) via covalent or non-covalent bonds. In some embodiments, the derivatized MaSp fibers bonded to the dye and / or pigment remain stable in the hair color composition.

[0312] In some embodiments, the hair color composition includes the derivatized porous MaSp fibers of the present invention, which are bound to a dye or pigment as a cosmetic active ingredient.

[0313] In some embodiments, the effective amount includes a w / w concentration of derivatized porous MaSp fibers in the hair color composition, which is 50-99.99(w / w)%, 50-60(w / w)%, 60-70(w / w)%, 70-80(w / w)%, 80-90(w / w)%, 90-92(w / w)%, 92-95(w / w)%, 95-97(w / w)%, 97-99(w / w)%, and 99-99.9(w / w)% (including any range in between).

[0314] In some embodiments, the effective amount includes a w / w concentration of derivatized porous MaSp fibers in the hair color composition, which is 0.01-95%, 0.01-0.1%, 0.1-0.5%, 0.5-0.1%, 0.1-0.5%, 0.5-1%, 1-5%, 5-10%, 10-20%, 20-30%, 30-50%, 50-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0315] In some embodiments, the hair color composition is characterized by a pH value of 3-7, 3-4, 4-5, 5-6, or 6-7 (including any range in between).

[0316] In some embodiments, the hair color composition is for coloring hair or for articles containing it (e.g., apparel, wigs, etc.). In some embodiments, the hair color composition adheres stably to the hair of the object that requires it. In some embodiments, the hair color composition provides a coating for hair. In some embodiments, the hair color composition can provide a stable coating for hair. In some embodiments, the hair color composition reduces or prevents the degradation of dyes and / or pigments (e.g., chemical degradation or photobleaching). In some embodiments, the coating is stable for at least 1 day(d), at least 5d, at least 10d, at least 15d, at least 20d, at least 25d, at least 30d (including any range in between).

[0317] While not bound by any particular theory or mechanism, it is assumed that human hair (bleached or unbleached) is negatively charged. Therefore, it is expected that a composition containing a positively charged polymer (for example, the hair color composition of the present invention) will form a coating on negatively charged hair by bonding to it (for example, via electrostatic interactions).

[0318] The inventors have successfully implemented hair color compositions (e.g., the hair color compositions described herein) containing various derivatized porous MaSp fibers. Some of these hair color compositions resulted in a uniform and stable coating of hair after contact with hair (e.g., human hair). Exemplary hair color compositions that successfully implemented hair coating include amination-MaSp fibers (e.g., chemically modified with 4-(2-aminoethyl)aniline;3-aminopropyl(amonipropyl)triethoxysilane or PEI). Those skilled in the art will understand that the zeta potential of amination-MaSp fibers is pH-dependent, meaning that amination-MaSp fibers have a positive zeta potential at pH less than the pKa of the corresponding amine (where pKa represents the pKa of the conjugated acid).

[0319] Furthermore, the inventors utilized various MaSp-based fibers for hair color compositions. Stable hair coating was obtained by using amination-MaSp-based proteins and amination-mutant MaSp-based proteins.

[0320] In some embodiments, the coating is stable after a series of washes (e.g., after 2, 4, 6, 8, 10, 15, or 20 washes, including any range in between). In some embodiments, the coating is characterized by reduced degradation (e.g., bleaching) compared to a control.

[0321] In some embodiments, the present invention relates to a kit comprising a medicated cosmetic composition. In certain embodiments, the medicated cosmetic composition is contained in a container. The container may be a bottle, a dispenser, or a package. The container may dispense a predetermined amount of the composition. In certain embodiments, the composition is dispensed as a spray, a dollar, or a liquid. The container may include markings on its surface. The markings may be words, abbreviations, pictures, or symbols.

[0322] Medicinal cosmetic composition (MaSp-based fiber in its original state) In another aspect of the present invention, there is a medicinal cosmetic composition comprising a MaSp polymer or MaSp fiber of the present invention (for example, the original MaSp polymer of the present invention and / or a derivatized MaSp polymer of the present invention) and a cosmetic active ingredient encapsulated or bound thereto. Where used herein, the terms “MaSp polymer” and “MaSp fiber” are to be used interchangeably herein.

[0323] In some embodiments, the medicated cosmetic composition of the present invention contains an effective amount of MaSp fibers or derivatized porous MaSp fibers. In some embodiments, the medicated cosmetic composition of the present invention contains an effective amount of MaSp fibers or derivatized porous MaSp fibers on a medicated cosmetic basis. In some embodiments, the medicated cosmetic composition of the present invention contains an effective amount of MaSp fibers on a medicated cosmetic basis and an effective amount of cosmetic active ingredients bound thereto on a medicated cosmetic basis.

[0324] In some embodiments, the composition of the present invention is a medicated cosmetic composition further comprising a cosmetically acceptable carrier. In some embodiments, the terms “composition of the present invention” and “medicated cosmetic composition of the present invention” are used interchangeably herein.

[0325] In some embodiments, the compositions of the present invention are formulated for application to the skin or hair of a target requiring it.

[0326] In some embodiments, the w / w concentration of the cosmetic active ingredient in the composition is 1-95%. In some embodiments, the w / w concentration of the cosmetic active ingredient in the composition is 1-5%, 5-10%, 10-15%, 15-20%, 20-30%, 30-35%, 35-40%, 40-45%, 45-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-80%, 80-90%, 90-95% (including any range or value between these).

[0327] In some embodiments, the cosmetic active ingredient is in contact with or bonded to MaSp fibers. In some embodiments, a polymer containing a large amount of the cosmetic active ingredient is physically bonded to the MaSp fibers. In some embodiments, the cosmetic active ingredient fills at least a portion of the pores on or within the MaSp fibers. In some embodiments, the cosmetic active ingredient is encapsulated by the MaSp fibers. In some embodiments, the cosmetic active ingredient is in contact with or bonded to small fibers. In some embodiments, the cosmetic ingredient is encapsulated by a twisted structure of particles (used herein as "matrix"). In some embodiments, the cosmetic active ingredient is encapsulated by particles. In some embodiments, the cosmetic active ingredient is incorporated into the MaSp fibers. In some embodiments, the cosmetic active ingredient is embedded within the MaSp fibers. In some embodiments, the cosmetic active ingredient is embedded within the matrix. In some embodiments, the matrix is ​​doped with the cosmetic active ingredient. In some embodiments, the cosmetic active ingredient is located within multiple pores. In some embodiments, the cosmetic active ingredient is located between small fibers. In some embodiments, the cosmetic active ingredient is located within a lumen, which is defined by the interwoven fibers of the matrix. In some embodiments, the cosmetic active ingredient is encapsulated by microfibers.

[0328] In some embodiments, the bond is via non-covalent bonding, physical interaction, or both.

[0329] In some embodiments, the cosmetic active ingredient fills 20% to 100% of the lumen volume. In some embodiments, the cosmetic active ingredient fills 55% to 100%, 60% to 100%, 55% to 100%, 70% to 100%, 75% to 100%, 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, 50% to 99%, 50% to 98%, 50% to 97%, 50% to 95%, 50% to 90%, 70% to 90%, or 70% to 95% (including any range in between).

[0330] In some embodiments, the cosmetic active ingredient fills 20% to 100% of the particle's volume (lumen). In some embodiments, the cosmetic active ingredient fills 55% to 100%, 60% to 100%, 55% to 100%, 70% to 100%, 75% to 100%, 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, 50% to 99%, 50% to 98%, 50% to 97%, 50% to 95%, 50% to 90%, 70% to 90%, or 70% to 95% (including any range in between).

[0331] In some embodiments, the content of MaSp fibers or derivatized MaSp fibers in the composition of the present invention is 20-60(w / w)%. In some embodiments, the content of the first polymer is 25-60(w / w)%, 30-60(w / w)%, 35-60(w / w)%, 30-40(w / w)%, 40-60(w / w)%, 40-50(w / w)%, 50-60(w / w)%, 40-45(w / w)%, 45-50(w / w)%, 50-55(w / w)%, 55-60(w / w)%, 20-55(w / w)%, or 20-50(w / w)% (including any range in between).

[0332] In some embodiments, the MaSp fiber content in the composition is 60-95(w / w)%, 60-70(w / w)%, 70-75(w / w)%, 75-80(w / w)%, 80-85(w / w)%, 85-90(w / w)%, 90-92(w / w)%, 92-95(w / w)%, 95-97(w / w)% (including any range in between).

[0333] In some embodiments, the content of MaSp fibers or derivatized MaSp fibers in the composition of the present invention (e.g., a medicinal cosmetic composition) is 0.1-20(w / w)%, 0.1-0.5(w / w)%, 0.5-1(w / w)%, 1-5(w / w)%, 5-10(w / w)%, 10-15(w / w)%, 15-20(w / w)% (including any range in between).

[0334] In some embodiments, the w / w ratio of the cosmetic active ingredient in the composition of the present invention to the MaSp fiber is 10:1 to 1:10, 10:1 to 8:1, 8:1 to 6:1, 6:1 to 4:1, 4:1 to 3:1, 3:1 to 2:1, 2:1 to 1:1, 1:1 to 1:2, 1:2 to 1:3, 1:3 to 1:5, 1:5 to 1:10 (including any range in between).

[0335] In some embodiments, the w / w ratio of the cosmetic active ingredient in the composition to the MaSp fibers is up to 6:1, up to 5:1, up to 4:1, up to 3:1, up to 2:1, and up to 1:1 (including any range in between).

[0336] In some embodiments, the composition of the present invention is a solid composition. In some embodiments, the composition of the present invention is in the form of pellets or powder. In some embodiments, the composition of the present invention is in the form of a film. In some embodiments, the composition of the present invention is in the form of a semi-solid (e.g., a gel or hydrogel). In some embodiments, the composition of the present invention is substantially homogeneous. In some embodiments, the cosmetic active ingredient and MaSp fibers are homogeneously mixed in the composition. In some embodiments, the composition (e.g., a solid composition) substantially lacks solvents, surfactants, carriers, particles, or combinations thereof, where substantially at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of the composition.

[0337] In some embodiments, the composition of the present invention further comprises 0.1% to 95% of a solvent, a film-forming agent, a pigment, a dye, a stabilizer, an oil, and a thickener, or any combination thereof.

[0338] In some embodiments, the composition of the present invention further comprises a solvent. In some embodiments, the w / w content of the solvent in the composition is 10-90%, 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0339] In some embodiments, the solvent is aqueous or organic solvent. In some embodiments, the organic solvent is as described herein.

[0340] In some embodiments, the compositions of the present invention are liquid or semi-liquid compositions. In some embodiments, the liquid or semi-liquid compositions are characterized by a viscosity of 50-3000 cP, 50-100 cP, 100-300 cP, 300-500 cP, 500-1000 cP, 1000-2000 cP, or 2000-3000 cP (including any range in between) at 25°C.

[0341] In some embodiments, the compositions of the present invention (e.g., liquid compositions) are selected from liquids, dispersants, emulsions, gels, hydrogels, semiliquids, and foams, or combinations thereof. In some embodiments, the compositions (e.g., liquid compositions) are substantially devoid of solvents, surfactants, carriers, particles, or combinations thereof, wherein the composition comprises substantially at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, and at least 99% by weight (including any range in between).

[0342] In some embodiments, the composition of the present invention (e.g., a liquid composition) further comprises a film-forming agent. In some embodiments, the w / w content of the film-forming agent in the composition is 0.1-20%, 0.1-1%, 1-2%, 2-5%, 5-7%, 4-6%, 6-8%, 8-10%, 10-12%, 12-15%, 15-20% (including any range between these). In some embodiments, the film-forming agent is selected from liquid film-forming agents and / or solid film-forming agents. In some embodiments, the film-forming agent is a solid film-forming agent.

[0343] Non-limiting examples of film-forming agents include, but are not limited to, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinyl acetate, polyalkyl acrylate; dextrin, cellulose derivatives, e.g., alkylcellulose and nitrocellulose, silicone-treated polysaccharides, e.g., pullulan tri(trimethylsiloxy)silylpropylcarbamate; pullulan, agave polysaccharides, polyphenols, gum; intansyl, acrylic silicone graft copolymers, e.g., alkyl acrylate-dimethicone copolymer, mineral oil, petroleum oil, vegetable oil, silicone resins, e.g., trimethylsiloxysilicate, silicone-modified polynorbornene, silicone resins, e.g., fluorine-modified silicone resins, fluorocarbon resins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, and polyurethanes, or any combination thereof.

[0344] Other non-limiting examples of film-forming agents include, but are not limited to, pullulan, tri(trimethylsiloxy)silylpropyl carbamate (e.g., TSPL-30d5), alkyl acrylate-dimethicone copolymer (e.g., KP-543, 545, 549, 550, and 545L), trimethylsiloxysilicate (e.g., KF-7312J and X-21-5250), and silicone-modified polynorbornene, or any combination thereof.

[0345] In some embodiments, the film-forming agent is in the form of a purified compound, a plant extract, at least a partially concentrated plant extract, or a combination thereof. In some embodiments, an appropriate concentration of the film-forming agent in the composition provides it with flexibility. In some embodiments, an appropriate concentration of the film-forming agent allows the composition to be applied to a control skin (e.g., by topical application). In some embodiments, an appropriate concentration of the film-forming agent enhances the film-forming properties of the composition. In some embodiments, an appropriate concentration of the film-forming agent is as described herein. Exemplary compositions containing the film-forming agent are provided in the Examples section.

[0346] In some embodiments, the composition of the present invention (e.g., a liquid composition) further comprises a thickening agent. In some embodiments, the w / w content of the thickening agent in the composition is 1-20%, 1-2%, 2-5%, 5-7%, 4-6%, 6-8%, 8-10%, 10-12%, 12-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range between these). In some embodiments, the thickening agent provides the liquid composition with a predetermined viscosity.

[0347] In some embodiments, the composition comprises MaSp fibers, a film-forming agent, and a cosmetic active ingredient. In some embodiments, the composition comprises 1-20 (w / w)% MaSp fibers, 0.1-10 (w / w)% film-forming agent, 1-70 (w / w)% cosmetic active ingredient, and optionally 10-95 (w / w)% solvent. In some embodiments, the composition comprises 5-15 (w / w)% MaSp fibers, 1-15 (w / w)% film-forming agent, 1-50 (w / w)% cosmetic active ingredient, and optionally 50-95 (w / w)% solvent. In some embodiments, the composition comprises 1-5% cosmetic active ingredient (an acid selected from, for example, α-hydroxycarboxylic acid, β-hydroxycarboxylic acid, citric acid, salicylic acid, etc.). Non-limiting exemplary compositions are described in the following Examples section of this specification.

[0348] In some embodiments, the composition further comprises additives. In some embodiments, the additives are selected from the group consisting of antimicrobial agents (e.g., methylparaben, propylparaben, butylparaben, ethylparaben, isobutylparaben, etc.) and skin conditioning agents (e.g., aloe extract, allantoin, bisabolol, ceramide, dimethicone, and dipotassium glycyrrhizate).

[0349] In some embodiments, the composition is a cosmetic formulation. In some embodiments, the cosmetic formulation contains ingredients suitable for use in cosmetics.

[0350] In some embodiments, the composition of the present invention is a solid composition. In some embodiments, the medicated cosmetic composition of the present invention is in the form of pellets or powder. In some embodiments, the medicated cosmetic composition of the present invention is in the form of a film. In some embodiments, the medicated cosmetic composition of the present invention is in the form of a semi-solid (e.g., a gel or hydrogel). In some embodiments, the medicated cosmetic composition of the present invention is substantially homogeneous. In some embodiments, the cosmetic active ingredient and the carrier are homogeneously mixed in the composition.

[0351] In some embodiments, the medicinal cosmetic composition (e.g., a solid composition) substantially lacks at least one of a solvent, a surfactant, a carrier, particles, or a combination thereof, where substantially at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of the composition.

[0352] In some embodiments, the medicinal cosmetic composition of the present invention further comprises 0.1 to 95% of a solvent, a film-forming agent, a pigment, a dye, a stabilizer, an oil, and a thickener, or any combination thereof.

[0353] In some embodiments, the medicinal cosmetic composition of the present invention further comprises a solvent. In some embodiments, the w / w content of the solvent in the composition is 10-90%, 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0354] In some embodiments, the solvent is aqueous or organic solvent. In some embodiments, the organic solvent is as described herein.

[0355] In some embodiments, the medicinal cosmetic composition of the present invention is a liquid or semi-liquid composition. In some embodiments, the liquid or semi-liquid composition is characterized by a viscosity of 50-3000 cP, 50-100 cP, 100-300 cP, 300-500 cP, 500-1000 cP, 1000-2000 cP, or 2000-3000 cP (including any range in between) at 25°C.

[0356] In some embodiments, the medicinal cosmetic composition of the present invention (e.g., a liquid composition) is selected from liquids, dispersants, emulsions, gels, hydrogels, semi-liquids, and foams, or combinations thereof. In some embodiments, the composition (e.g., a liquid composition) is substantially devoid of solvents, surfactants, carriers, particles, or combinations thereof, wherein substantially the composition comprises at least 80% by weight, at least 90% by weight, at least 92% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, and at least 99% by weight (including any range in between).

[0357] In some embodiments, the medicinal cosmetic composition (e.g., a liquid composition) of the present invention further comprises a thickening agent. In some embodiments, the w / w content of the thickening agent in the composition is 1-20%, 1-2%, 2-5%, 5-7%, 4-6%, 6-8%, 8-10%, 10-12%, 12-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, 90-95% (including any range or value between these). In some embodiments, the thickening agent provides the liquid composition with a predetermined viscosity.

[0358] In some embodiments, the medicated cosmetic composition further comprises additives. In some embodiments, the additives are selected from the group consisting of antimicrobial agents (e.g., methylparaben, propylparaben, butylparaben, ethylparaben, isobutylparaben, etc.) and skin conditioning agents (e.g., aloe extract, allantoin, bisabolol, ceramide, dimethicone, and dipotassium glycyrrhizate).

[0359] In some embodiments, the medicated cosmetic composition is a cosmetic formulation. In the embodiments, the cosmetic formulation contains ingredients suitable for use in cosmetics.

[0360] In some embodiments, the medicated cosmetic composition is a sunscreen composition. In some embodiments, the sunscreen composition is intended to absorb at least a portion of UV radiation. In some embodiments, the sunscreen composition is intended to reduce UV exposure to the skin and / or hair in question.

[0361] In some embodiments, UV exposure is reduced by at least 20%, at least 30%, at least 50%, at least 70%, at least 90%, at least 95%, and at least 99% (including any range in between).

[0362] In some embodiments, the sunscreen composition is characterized by an SPF of 1-100, 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-100 (including any range in between).

[0363] In some embodiments, the effective amount comprises a sufficient amount of the MaSp fibers of the present invention to obtain a reduction in UV exposure, the reduction being as described herein. In some embodiments, the effective amount comprises a w / w concentration of the MaSp fibers of the present invention in a sunscreen composition of 0.01-95%, 0.01-0.1%, 0.1-0.5%, 0.5-0.1%, 0.1-0.5%, 0.5-1%, 1-5%, 5-10%, 10-20%, 20-30%, 30-50%, 50-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0364] In some embodiments, the medicated cosmetic composition is formulated for application to the hair in question and is also referred to herein as “hair composition.” In some embodiments, the hair composition contains an effective amount of the MaSp fibers of the present invention bound to a dye and / or pigment. In some embodiments, the medicated cosmetic composition is a hair composition containing an effective amount of the derivatized porous MaSp fibers of the present invention bound to a dye and / or pigment.

[0365] In some embodiments, the hair composition comprises an effective amount of the MaSp fibers of the present invention bonded to a dye and / or pigment, wherein the bond is via a covalent or non-covalent bond. In some embodiments, the hair composition comprises any derivatized MaSp fibers (e.g., porous MaSp fibers and / or non-porous MaSp fibers) covalently bonded to a functional group described herein (e.g., a positively or negatively charged group). In some embodiments, the MaSp fibers bonded to the dye and / or pigment remain stable in the hair composition.

[0366] In some embodiments, the hair composition includes the MaSp-based fibers of the present invention bound to a dye or pigment as a cosmetic active ingredient.

[0367] In some embodiments, the effective amount includes a w / w concentration of MaSp fibers (e.g., derivatized or original porous MaSp fibers) in the hair composition, which is 50-99.99(w / w)%, 50-60(w / w)%, 60-70(w / w)%, 70-80(w / w)%, 80-90(w / w)%, 90-92(w / w)%, 92-95(w / w)%, 95-97(w / w)%, 97-99(w / w)%, or 99-99.9(w / w)% (including any range in between).

[0368] In some embodiments, the effective amount includes the w / w concentration of MaSp fibers in the hair composition, which is 0.01-95%, 0.01-0.1%, 0.1-0.5%, 0.5-0.1%, 0.1-0.5%, 0.5-1%, 1-5%, 5-10%, 10-20%, 20-30%, 30-50%, 50-70%, 70-80%, 80-90%, 90-95% (including any range in between).

[0369] In some embodiments, the hair composition is characterized by a pH value of 3-7, 3-4, 4-5, 5-6, or 6-7 (including any range in between).

[0370] In some embodiments, the hair composition is for coloring the target hair. In some embodiments, the hair composition adheres stably to the target hair that requires it. In some embodiments, the hair is damaged hair. In some embodiments, the hair composition has a higher affinity for damaged hair compared to undamaged hair, as shown in Figure 1.

[0371] While not bound by any particular theory or mechanism, it is assumed that damaged human hair (bleached or unbleached) is negatively charged. Therefore, it is expected that a composition containing a positively charged polymer (e.g., the hair composition of the present invention) will form a coating on negatively charged damaged hair by bonding to it (e.g., via electrostatic interactions).

[0372] As used herein, the term “damaged hair” refers to any physical damage to the hair, such as damage to the hair scales / cuticles. In some embodiments, the hair scales / cuticles of damaged hair are jagged, with some of them lifted or broken. In some embodiments, the outer layer of damaged hair is stripped, and the inner cortex is unprotected and fragile in some areas of the hair fibers. In some embodiments, the outer layer of damaged hair is almost completely removed, where the cortex is exposed and / or weakened. Damaged hair may be characterized by a dull appearance, uneven color balance, or a rough texture with faded color. Furthermore, damaged hair may be characterized by split ends.

[0373] In some embodiments, the hair composition provides a coating for hair. In some embodiments, the hair composition can provide a stable coating for hair. In some embodiments, the hair composition reduces or prevents the degradation of dyes and / or pigments (e.g., chemical degradation or photobleaching).

[0374] In some embodiments, the hair composition prevents or reduces hair damage.

[0375] In some embodiments, the coating is stable for at least 1 day(d), at least 5d, at least 10d, at least 15d, at least 20d, at least 25d, and at least 30d (including any range in between).

[0376] The inventors have successfully implemented hair compositions containing various derivatized porous MaSp fibers and hair compositions containing porous MaSp fibers in their original state (e.g., the hair compositions described herein). Some of these hair compositions resulted in a uniform and stable hair coating after contact with hair (e.g., human hair). Exemplary hair compositions that have successfully implemented hair coating (see, for example, Figures 1-9) include amination-MaSp fibers (e.g., chemically modified with 4-(2-aminoethyl)aniline; 3-aminopropyl(amonipropyl)triethoxysilane or PEI). Those skilled in the art will understand that the zeta potential of amination-MaSp fibers is pH-dependent, and therefore amination-MaSp fibers have a positive zeta potential at pH less than the pKa of the corresponding amino acid (where the pKa value represents the pKa of the conjugated acid).

[0377] In some embodiments, the hair composition comprises 0.5 to 5 (w / w)% of aminated MaSp fibers, where amination is as described herein. In some embodiments, the hair composition comprises 2.5 to 5 (w / w)% of aminated MaSp fibers.

[0378] Furthermore, the inventors utilized various MaSp-based fibers for hair compositions. Stable hair coatings were obtained by using amination-MaSp-based proteins and amination-mutant MaSp-based proteins.

[0379] In some embodiments, the hair composition prevents or reduces damage to hair, where damage relates to exposure to conditions selected from UV irradiation, thermal radiation, environmental pollutants, oxidizing agents, reducing agents, irritants, or any combination thereof. In some embodiments, the prevention or reduction is at least 20%, at least 30%, at least 50%, at least 70%, at least 90%, at least 95%, or at least 99% (including any range in between) compared to a control. In some embodiments, the control is in its original state (e.g., untreated hair). In some embodiments, the control includes hair treated with a commercially available hair composition.

[0380] In some embodiments, the hair composition substantially retains the initial physical properties (e.g., mechanical strength) of the hair after contact with it, substantially as described herein.

[0381] In some embodiments, the hair composition prevents or reduces damage to the hair after exposure to thermal radiation (e.g., a temperature of about 200°C), as shown in Figure 2.

[0382] In some embodiments, the hair composition substantially retains the water content of the hair after contact with it, as shown in Figure 3.

[0383] In some embodiments, the hair composition prevents or reduces damage to hair after exposure to hair-damaging chemical compositions such as oxidizing or reducing agents (e.g., chlorine, hypochlorous acid aqueous solution), seawater, or a combination thereof. Figure 4 illustrates the retention of mechanical strength in hair treated with the hair composition of the present invention after exposure to chlorinated water and / or seawater.

[0384] In some embodiments, the hair composition prevents or reduces damage to hair after exposure to environmental pollutants, such as dust, as illustrated in Figure 5.

[0385] In some embodiments, the hair composition prevents or reduces fading or bleaching of colored or uncolored hair (after exposure to chemical compositions such as oxidizing or reducing agents, and / or seawater; after exposure to UV irradiation), as illustrated by Figures 6 and 7. In some embodiments, the hair composition prevents or reduces oxidation of treated hair.

[0386] In some embodiments, the coating is stable after a series of washes (e.g., 2, 4, 6, 8, 10, 15, 20 washes (including any range in between)). In some embodiments, the coating is characterized by reduced degradation (e.g., bleaching) compared to a control, as illustrated by Figures 6 and 7.

[0387] In some embodiments, the hair composition modifies the shape of the hair in contact with it (e.g., hair straightening or curling), as illustrated by Figures 8 and 9. In some embodiments, the hair composition substantially retains the shape of the hair in contact with it, where the hair composition comprises 0.2–0.7 (w / w)% of the MaSp-type proteins of the present invention (e.g., amination-type MaSp-type proteins, or unmodified or original MaSp-type proteins), as illustrated by Figures 9 and 10, respectively. In some embodiments, the hair composition induces curling of the hair in contact with it.

[0388] In some embodiments, the compositions of the present invention are substantially stable within the medicinal cosmetic composition.

[0389] In some embodiments, the medicated cosmetic composition is biocompatible. In some embodiments, the medicated cosmetic composition enhances the bioaccessibility of hydrophobic or hydrophilic cosmetic active ingredients. In some embodiments, the medicated cosmetic composition enhances the bioaccessibility of a compound in which the compound is a cosmetic active ingredient selected from (as illustrated below herein) polysaccharides, α-hydroxycarboxylic acids, hygroscopic agents, etc. The term “bioaccessibility,” as used herein, refers to the property of any one of the compositions of the present invention to release a cosmetic active ingredient in vitro. Release in vitro can be evaluated using a skin tape test (described in the Examples section).

[0390] In some embodiments, the medicated cosmetic composition increases the bioavailability and / or bioaccessibility of the cosmetic active ingredients. In some embodiments, the derivatized MaSp-based fibers substantially reduce the degradation of the cosmetic active ingredients embedded within them.

[0391] In some embodiments, the medicinal cosmetic composition of the present invention is in the form of a cosmetic. In some embodiments, the medicinal cosmetic composition of the present invention is in the form of a composition that can be diffused locally, a sprayable composition, an aerosolized composition, an injectable composition, an edible composition, a tablet, a gel capsule, or a pill.

[0392] In some embodiments, the medicinal cosmetic composition contains 0.1 to 20% by weight of the MaSp-based fibers of the present invention. In some embodiments, the medicinal cosmetic composition contains 0.3 to 0.5% by weight, 0.5 to 1% by weight, 1 to 5% by weight, 5 to 10% by weight, and 10 to 15% by weight of the MaSp-based fibers of the present invention. In some embodiments, the medicinal cosmetic composition contains 0.3 to 0.5% by weight, 0.5 to 1% by weight, 1 to 5% by weight, 5 to 10% by weight, and 10 to 15% by weight of the original (e.g., unmodified) MaSp-based fibers of the present invention and a cosmetically acceptable carrier.

[0393] In some embodiments, the composition is characterized by a longer release of the cosmetic active ingredient from the composition compared to a control. In some embodiments, the composition is characterized by a stepwise release of the cosmetic active ingredient from there. In some embodiments, the composition is characterized by a sustained release of the cosmetic active ingredient from there.

[0394] In some embodiments, the cosmetic active ingredient is released under physiological conditions. In some embodiments, the cosmetic active ingredient is released after contact with the target skin. In some embodiments, the cosmetic active ingredient is released in an aqueous solution.

[0395] In some embodiments, the release rate of the cosmetic active ingredient from the composition is at least 10% lower compared to the control. In some embodiments, the release rate of the cosmetic active ingredient from the composition is at least 10%, at least 20%, at least 30%, at least 50%, at least 70%, at least 90%, at least 100%, at least 150%, at least 200%, at least 250%, at least 300%, at least 400%, at least 450%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% lower (including any range or value in between).

[0396] In some embodiments, the control is a polymer. In some embodiments, the control lacks MaSp system proteins. In some embodiments, the control is a silk protein or polysaccharide (e.g., cellulose). As illustrated below herein (Figures 20, 21, and 22), the compositions of the present invention are characterized by an improved release profile (i.e., lower release rate) of the cosmetic active ingredient compared to controls (e.g., cellulose and silk proteins).

[0397] In some embodiments, the release period is extended by at least 50%, at least 100%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, and at least 1000% (including any range or value in between) compared to the control.

[0398] In some embodiments, the composition is biocompatible. In some embodiments, the composition enhances the bioaccessibility of hydrophobic or hydrophilic cosmetic active ingredients. In some embodiments, the composition enhances the bioaccessibility of a compound, where the compound is a cosmetic active ingredient selected from polysaccharides, α-hydroxycarboxylic acids, hydrating agents, etc. (as illustrated herein). The term “bioaccessibility,” as used herein, refers to the property of any one of the compositions of the present invention to release a cosmetic active ingredient in vitro. In vitro release can be evaluated using a skin tape test (described in the Examples section).

[0399] In some embodiments, the composition increases the bioavailability and / or bioaccessibility of cosmetic active ingredients. In some embodiments, cosmetic active ingredients bound to or encapsulated by MaSp fibers are characterized by higher stability compared to cosmetic active ingredients in their original state (e.g., unencapsulated). In some embodiments, MaSp fibers substantially reduce the degradation of cosmetic active ingredients. In some embodiments, MaSp fibers substantially reduce the degradation of cosmetic active ingredients, where degradation is related to chemical or physical damage (e.g., oxidation, free radicals, UV irradiation), as illustrated in Figures 11-12.

[0400] In some embodiments, the composition increases the retention time of cosmetic active ingredients on the skin, as illustrated in Figure 13.

[0401] In some embodiments, the compositions of the present invention are in the form of locally diffusible compositions, sprayable compositions, aerosolized compositions, injectable compositions, edible compositions, tablets, gel capsules, or pills.

[0402] In some embodiments, the present invention relates to a kit comprising the composition. In certain embodiments, the composition is contained in a container. The container may be a bottle, a dispenser, or a package. The container may dispense a predetermined amount of the composition. In certain embodiments, the composition is dispensed as a spray, a dollop, or a liquid. The container may include markings on its surface. The markings may be words, abbreviations, pictures, or symbols. In another embodiment, there is a sunscreen composition containing an effective amount of the complex of the present invention.

[0403] In one embodiment, the sunscreen composition of the present invention further comprises a carrier.

[0404] In one embodiment, the sunscreen composition of the present invention has an SPF value of 1 to 100.

[0405] In one embodiment, the effective amount includes the w / w concentration of the complex in a sunscreen composition of 10(w / w)% to 50(w / w)%.

[0406] In one embodiment, the sunscreen composition of the present invention is in the form of a cosmetic.

[0407] In another embodiment, there is a hair color composition comprising an effective amount of any one of the derivatized porous MaSp fibers of the present invention bound to a dye or pigment.

[0408] In one embodiment, the hair color composition includes a carrier.

[0409] In one embodiment, the effective amount includes the w / w concentration of derivatized porous MaSp fibers in a hair color composition of 50-99.9% (w / w).

[0410] In one embodiment, the hair color composition is characterized by a pH value of 3 to 7.

[0411] In one embodiment, the hair color composition is in the form of a cosmetic product.

[0412] Medicinal cosmetic ingredients As used herein, the terms “MaSp fiber” and “porous MaSp fiber” are to be used interchangeably.

[0413] In some embodiments, the composition is a complex comprising MaSp-based fibers bound to a cosmetic active ingredient, where the binding is via non-covalent bonds, covalent bonds, physical interactions, or a combination thereof.

[0414] In some embodiments, the cosmetic active ingredient includes compounds selected from the group consisting of polysaccharides, sunscreens, humectants, antioxidants, essential oils, vitamins (e.g., A, B, B3, B12, C, D, E, and K), acids (including α-hydroxycarboxylic acids and β-hydroxycarboxylic acids as described later herein), plant extracts, scrubbing agents, or any combination thereof. In some embodiments, the cosmetic active ingredient is a biologically effective compound. Biologically effective compounds are well known in the art.

[0415] In some embodiments, the cosmetic active ingredient is in the form of a purified compound, a plant extract, at least partially concentrated plant extract, or a combination thereof.

[0416] Non-exclusive examples of polysaccharides include, but are not limited to, hyaluronic acid and / or its salts, alginic acid and / or its salts, chitosan containing any derivative (e.g., salts), or any combination thereof.

[0417] Other useful polysaccharides include scleroglucans, which contain branched chains of (1-3) linked glucose units with (1-6) linked glucose units for every three units.

[0418] In some embodiments, the sunscreen is a UV absorber and / or UV reflector that may be used in a composition of the present invention, which includes a chemical sunscreen cream and / or a physical sunscreen cream.

[0419] As a non-exclusive example of chemical sunscreen creams, but not limited to, para-aminobenzoic acid (PABA), PABA esters (glyceryl PABA, amyldimethyl PABA, and octyldimethyl PABA), butyl PABA, ethyl PABA, ethyl dihydroxypropyl PABA, benzophenones (oxybenzone, surisobenzone, benzophenone, and benzophenone-1 to 12), cinnamates (octyl methoxycinnamate, isoamyl p-methoxycinnamate, octyl methoxycinnamate, cinoxate, diisopropyl Methyl cinnamate, DEA-methoxy cinnamate, ethyl diisopropyl cinnamate, glyceryl octanoate dimethoxy cinnamate, and ethyl methoxy cinnamate), cinnamate esters, salicylates (homomethylsalicylate, benzylsalicylate, glycolsalicylate, isopropylbenzylsalicylate, etc.), anthranilates, ethyl urocanate, homosalate, octisalate, dibenzoylmethane derivatives (e.g., avobenzone), octocrylene, octyltriazone, digalloyl trioleate (digalloy Examples include trioleate, glycerylaminobenzoate, lauson containing dihydroxyacetone, ethylhexyl triazone, dioctylbutamide triazone, benzylidenemalonate polysiloxane, terephthalylidene dicamphor sulfonic acid, phenyldibenzimidazole disodium tetrasulfonate, diethylamino hydroxybenzoylhexyl benzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazoylphenylethylhexyliminotriazine, drometrizole trisiloxane, methylenebis-benzotriazolyltetramethylbutyl(butyi)phenol, and bis-ethylhexyloxyphenol methoxyphenyl triazine, 4-methylbenzylidene camphor, and isopentyl 4-methoxycinnamate (including any derivatives (e.g., salts) or any combination thereof).

[0420] Non-exclusive examples of physical sunscreens include, but are not limited to, kaolin, talc, petrolatum, and metal oxides (e.g., titanium dioxide and zinc oxide), or any combination thereof.

[0421] The compositions of the present invention may have UVA and UVB absorption properties. The compositions may have a sunscreen index (SPF) of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90 or higher (including any range or value between them).

[0422] Non-exclusive examples of water-retaining agents include, but are not limited to, retinol, retinyl acetate, amino acids, lactic acid, chondroitin sulfate, diglycerin, erythritol, fructose, glucose, glycerin (or glycerol), glycerol ethylene glycol, propylene glycol, 12,6-hexanetriol, honey, hydrogenated honey, hydrogenated starch hydrolysate, inositol, lactitol, maltitol, maltose, mannitol, natural moisturizing ingredients, polyethylene glycol (PEG), PEG-15 butanediol, polyglyceryl sorbitol, propylene glycol, sorbitol, sucrose, trehalose, urea, and xylitol (including any derivatives (e.g., salts) or any combination thereof).

[0423] Other examples of water-retaining agents, though not limited to them, include acetylated lanolin, enzymes, acetylated lanolin alcohol, acrylate / C10-30 alkyl acrylate crosspolymer, acrylate copolymer, algae extract, aloe vera (aloe-barbadensis) extract, apricot kernel oil, ascorbic acid, ascorbyl palmitate, avocado oil, barrier sphingolipids, butyl alcohol, beeswax, behenyl alcohol, β-sitosterol, birch bark extract, borage extract, butcher's broom extract, butylene glycol, Calendula officinalis oil, candelilla (Euphorbia cerifera) wax, canola oil, caprylic / capric triglyceride, cardamom oil, carnauba wax, carrageenan (Chondrus crispus), and carrot (Daucus carota) Sativa oil, castor oil, ceramide, ceresin, ceteareth-5, ceteareth-12, ceteareth-20, cetearyl octanoate, ceteth-20, ceteth-24, cetyl acetate, cetyl octanoate, cetyl palmitate, chamomile oil, cholesterol, cholesterol ester, cholesteryl hydroxysteart, salvia (Salvia sclarea) oil, cocoa butter, (caprylic / capric acid) coconut alkyl, coconut (Cocos nucifera) oil, collagen, collagen amino acids, corn (Zea Mays oil, fatty acids, decyl oleate, dextrin, diazolidinyl urea, dimethicone copolyol, dimethiconol, dioctyl adipate, dioctyl succinate, dipentaerythrityl hexacaprate / hexacaprate, DMDM ​​hydantoin, erythritol, ethoxydiglycol, ethyl linoleate, Eucalyptus globulus oil, evening primrose oil, fatty acids, fructose, gelatin, Geranium maculatumMaculatum oil, glucosamine, glucose glutamate, glutamic acid, glycereth-26, glycerin, glycerol, glyceryl distearate, glyceryl hydroxystearate, glyceryl laurate, glyceryl linoleate, glyceryl myristate, glyceryl oleate, glyceryl stearate, glyceryl stearate, glycol stearate, glycosaminoglycan, grape seed (Vitis vinifera) oil, hazelnut (Corylus americana) oil, hexylene glycol, hybrid safflower (Carthamus) Tinctorius oil, hydrogenated castor oil, hydrogenated cocoglycerides, hydrogenated coconut oil, hydrogenated lanolin, hydrogenated lecithin, hydrogenated palm glycerides, hydrogenated palm kernel oil, hydrogenated soybean oil, hydrogenated animal fat glycerides, hydrogenated vegetable oil, hydrolyzed collagen, hydrolyzed elastin, hydrolyzed glycosaminoglycans, hydrolyzed keratin, hydrolyzed soybean protein, hydroxylated lanolin, hydroxyproline, imidazolidinyl urea, iodopropynyl butylcarbamate, isocetyl stearate, isocetyl stearoyl stearate, Isodecyl oleate, isopropyl isostearate, isopropyl lanolate, isopropyl myristart, isopropyl palmitate, isopropyl stearate, isostearamide DEA, isostearic acid, isostearyl lactate, isostearyl neopentanoate, jasmine oil, jojoba oil, kelp, kukui oil, lactamide MEA, laeth-16, laeth-10 acetate, lanolin, lanolinic acid, lanolin alcohol, lanolin oil, lanolin wax, lavender oil, lecithin, lemon (Citrus medica limonum) oil, linoleic acid, linolenic acid, macadamia nut oil, magnesium stearate, magnesium sulfate, maltitol, chamomile (Chamomilla)Recutita oil, glucose methylsesquistearate, microcrystalline wax, mineral oil, mink oil, Mortierella oil, myristyl lactate, myristyl myristart, myristyl propionate, neopentyl glycol dicaprylate / dicaprate, octyldodecanol, octyldodecyl myristart, octyldodecyl stearoyl stearate, octyl hydroxystearate, octyl palmitate, octyl salicylate, octyl stearate, oleic acid, olive (Olea europaea) oil, orange (Citrus aurantium dulcis) oil, palm (Elaeis guineensis) oil, palmitic acid, pantethine, panthenol, panthenyl ethyl ether, paraffin, peach kernel (Prunus persica) oil, peanut (Arachis hypogaea) oil, PEG-8C12-18 ester, PEG-15 cocamine, PEG-150 distearate, PEG-60 glyceryl isosteartrate, PEG-5 glyceryl steartrate, PEG-30 glyceryl steartrate, PEG-7 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-20 methyl glucose sesquisteartrate, PEG-40 sorbitan peroleate, PEG-5 soybean sterols, PEG-10 soybean sterols, PEG-2 steartrate, PEG-8 steartrate, PEG-20 steartrate, PEG-32 steartrate, PEG-40 steartrate, PEG-50 steartrate, PEG-100 steartrate, PEG-150 steartrate, pentadecalactone, peppermint oil, petrolatum, ri Lipids, polyamino sugar concentrate, polyglyceryl-3 diisostearate, polyquaternium-24, polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, polysorbate 85, potassium myristate, potassium palmitate, potassium sorbate, potassium stearate, propylene glycol, propylene glycol dicaprylate / dicaprate, propylene glycol dioctanoate, propylene glycol diperargonate, propylene glycol laurate, propylene glycol stearate, propylene glycol stearate SE, PVP, pyridoxine dipalmitate, quaternium-15, quaternium-18 hectorite, quaternium-22, retinyl palmitate, rice bran (Oryza Sativa oil, rosemary oil, rose oil, safflower (Carthamus tinctorius) oil, sage (Salvia officinalis) oil, sandalwood (Santalum album) oil, serum protein, sesame (Sesamum indicum) oil, shea butter, sodium chondroitin sulfate, sodium palmitate, sodium PCA, sodium polyglutamate, sodium stearate, soluble collagen, sorbic acid, sorbitan laurate, sorbitan oleate, sorbitan palmitate, sorbitan sesquioleate, sorbitan stearate, sorbitol, soy (GlycineExamples include soybean oil, sphingolipids, squalane, squalene, stearoamide MEA-steart, stearic acid, stearoxide dimethicone, stearoxide trimethylsilane, stearyl alcohol, stearyl glycyrrhetinate, stearyl heptanoate, stearyl steart, sunflower seed (Helianthus annuus) oil, sweet almond oil, synthetic beeswax, tocopherol, tocopheryl acetate, tocopheryl linoleate, tribehenin, tridecyl neopentanoate, tridecyl stearate, triethanolamine, tristearin, water, wax, wheat germ (Triticum vulgare) oil, and ylang-ylang oil (including any derivatives thereof (e.g., salts) or any combination thereof).

[0424] As non-exclusive examples of antioxidants, but not limited to them, acetylcysteine, ascorbic acid, polypeptides (e.g., dipeptide-2, palmitoyl tripeptide-5, palmitoyl oligopeptide / palmitoyl hexapeptide, carnosine, pentapeptide-18), ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, BHA, DMAE (dimethylaminoethanol), BHT, t-butylhydroquinone, diamylhydroquinone, di-t-butylhydroquinone, dicetylthiodipropionate, dioleyltocopherylmethylsilanol, disodium ascorbyl sulfate, distearylthiodipropionate, ditridecylthiodipropionate, dodecylgalate, erythorbic acid, and ascorbic acid esters. Ethyl ferulate, ferulic acid, gallic acid ester, hydroquinone, isooctyl thioglycolate, kojic acid, magnesium ascorbate, magnesium ascorbyl phosphate, methylsilanol ascorbate, natural plant antioxidants, such as green tea or grape seed extract, nordihydroguaiaretic acid, octyl gallate, phenylthioglycolic acid, potassium (ascorbyl / tocopheryl) phosphate, potassium sulfite, propyl gallate, quinone, rosmarinic acid, sodium ascorbate, sodium bisulfate, sodium erythorbate, sodium pyrosulfite, sodium sulfite, superoxide dismutase, sodium thioglycolate, sorbityl furfural, thiodiglycol, thiodiglycolamide, thiodiglycolic acid, thioglycolic acid, thiolactic acid Examples include tocopherol, tocopheryl acid, thiosalicylic acid, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50, tocopherol, tocophersolane, tocopheryl acetate, tocopheryl linoleate, tocopheryl nicotinate, tocopheryl succinate, and tris(nonylphenyl) phosphite (including any of their derivatives (e.g., salts) or any combination thereof).

[0425] As non-exclusive examples of plant extracts, but not limited to them, include: kidney bean (Haseolus vulgaris), avocado (Persea Americana), apricot (Prunus armeniaca), arnica montana (Arnica montana), hollyhock (Althea officinalis), orange (Citris sinensis), lemon (Citrus medica limonum), sweet orange (Citrus aurantium dulcis), peppermint (Mentha piperita), European white birch (Betula alba), borage (Borago officinalis), rusticus (Ruscus aculeatus), calendula (Calendula officinalis), three-leaved beach turkey (Wedelia trilobata), carnauba palm (Copernicia cerifera), and castor bean (Ricinus) Communis), Cardamomum (Elettaria cardamomum), Rosemary (Rosmarinus officinalis), Burretiodendron hsienmu, Cacao (Theobroma cacao), Jasmine (Jasminum officinale), Evening Primrose (Oenothera biennis), European Grape (Vitis vinifera), Roman Chamomile (Anthemis nobilis), Shea Butter Tree (Butyrospermum parkii), Almond (Prunus amygdalus dulcis), Kukui (Aleurites moluccana), Lavender (Lavandula angustifolia), Jojoba (Buxus chinensis), Bauhinia brachycarpa var.Cavaleriei, Cystacanthus paniculatus, Caesalpinia minax, Cananga odorata, Pueraria wallichii, Tetracentron sinense, Bridlia insulana, Hedyotis verticillata, Syzygium fruticosum, Chamomile (Chamomilla recutita), Cercidiphyllum japonicum, Bauhinia glauca, Rhododendron siderophyllum, Cudrania pubescens, Cajanus cajan, Wendlandia uvariifolia, Aloe vera, Aloe-barbadensis, Siegesbeckia glabrescens), red duckweed (Azolla imbricate), dwarf duckweed (Juncus bufonius), Poikilospermum suaveolens, Amakusagi (Clerodendrum trichotomum var.fargesii), Porandra ramosa, pound apple (Annona glabra), Sterculia pexa, Phoebe puwenensis, Myriopteron extensum, Croton lachnocarpa, Dillenia turbinata, Alpinia blepharocalyx, Crotalaria spectabilis, Ficus lacor, Ravenala Madagascariensis), Cocculus orbiculatus, Panax ginseng, Drynaria fortunei, Acrachne racemosa, Pseuderanthemum polyanthum, Eriobotrys serrata, Vernonia arborea, Adianthum caudatum, Phaseolus lunatus), Ipomoea Examples include *Cairica*, *Alopecurus aequalis*, *Arenga pinnata*, *Rhynchosia yunnanensis*, *Syzygium cumini*, *Clausena dunniana*, *Cyclosurus parasiticus*, and *Solanum carolinense*, or any combination thereof.

[0426] In some embodiments, the composition comprises plants, plant parts, and / or extracts thereof. Plant parts may be the whole plant or parts of the plant (e.g., roots, bark, sap, stems, leaves, flowers, seeds, leaves, stems, roots, flowers, seeds, sap, bark, etc.).

[0427] In some embodiments, the extract is a whole plant extract. In some embodiments, the extract is an extract of a part of the plant (e.g., root, bark, sap, stem, leaves, flowers, seeds, leaves, stem, root, flowers, seeds, sap, bark, etc.). In some embodiments, the extract is an aqueous or non-aqueous extract. In some embodiments, the non-aqueous extract includes an organic solvent (e.g., methanol, ethanol, propanol, butanol, chloroform, dichloromethane, chlorobenzene, propylene glycol, ethylene glycol, ethyl acetate, DMF, DMSO, etc.) and an oil, or a combination thereof.

[0428] Essential oils include oils derived from herbs, flowers, trees, and other plants. Such oils typically exist as tiny droplets between plant cells and can be extracted by several methods known to those skilled in the art (e.g., steam distillation, enfleurage (i.e., extraction using fats), maceration, solvent extraction, or mechanical pressurization). These types of oils tend to evaporate when exposed to air (i.e., volatile oils). As a result, many essential oils are colorless but can oxidize over time and become darker in color. Essential oils are insoluble in water but soluble in organic solvents such as alcohol, ether, fixative oils (vegetable), and other organic solvents. Essential oils are usually named after the plant from which the oil is found. For example, rose oil or peppermint oil are derived from rose or peppermint, respectively. Non-limiting examples of essential oils that may be used in the context of the present invention include sesame oil, macadamia nut oil, tea tree oil, evening primrose oil, Spanish sage oil, rosemary oil, coriander oil, thyme oil, and pimento oil. Examples include berry oil, rose oil, anise oil, balsam oil, bergamot oil, rosewood oil, cedar oil, chamomile oil, sage oil, clary sage oil, clove oil, cypress oil, eucalyptus oil, fennel oil, sea fennel oil, frankincense oil, geranium oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lavender oil, lemon oil, lemongrass oil, lime oil, mandarin oil, marjoram oil, myrrh oil, neroli oil, orange oil, patchouli oil, pepper oil, black pepper oil, petitgrain oil, pine oil, rose otto oil, rosemary oil, sandalwood oil, spearmint oil, spikenard oil, vetiver oil, wintergreen oil, or ylang-ylang. Other essential oils known to those skilled in the art are also intended to be useful in the context of the present invention.

[0429] Non-limiting examples of scrubbing agents include, but are not limited to, salicylic acid, citric acid, α-hydroxycarboxylic acids (e.g., lactic acid, glycolic acid, lactobionic acid, tartaric acid, malic acid), and β-hydroxycarboxylic acids (e.g., propionic acid, α-hydroxypropionic acid, β-hydroxypropionic acid, β-hydroxybutyric acid, β-hydroxy, β-methylbutyric acid, and carnitine), as well as acids (e.g., azelaic acid, oleic acid, linoleic acid, kojic acid, ferulic acid, mandelic acid, shikimic acid) (including salts of any of these or any combination thereof).

[0430] Other cosmetic active ingredients are widely used in cosmetic formulations and are well known to those skilled in the art. In some embodiments, the cosmetic active ingredient substantially lacks any further biologically active ingredients. In some embodiments, the cosmetic active ingredient of the present invention essentially consists of the compounds listed above herein. In some embodiments, the cosmetic active ingredient substantially lacks MaSp fibers. In some embodiments, the cosmetic active ingredient substantially lacks proteins.

[0431] Goods In another embodiment of the present invention, there is an article comprising the composition of the present invention. In some embodiments, the article is a topical care product. In some embodiments, the article is a cosmetic (e.g., a color cosmetic, powder, or face cleanser).

[0432] Cosmetics may be cosmetics described in other sections of this specification or cosmetics known to those skilled in the art. Non-exclusive examples of cosmetics include moisturizers, creams, lotions, emollients, foundations, night creams, lipsticks, cleansers, cosmetics, sunscreens, masks, anti-aging products, deodorants, antiperspirants, perfumes, colognes, and the like.

[0433] In some embodiments, the article comprises the composition and carrier of the present invention. In some embodiments, the carrier is a physiologically suitable carrier. Exemplary physiologically suitable carriers are listed below herein, and further physiologically suitable carriers are well known in the art.

[0434] In some embodiments, the carrier includes an emulsifier. The emulsifier can reduce interphase tension and improve the formulation and stability of the emulsion. The emulsifier can be nonionic, cationic, anionic, or amphoteric (see McCutcheon's (1986); U.S. Patents No. 5,011,681; No. 4,421,769; No. 3,755,560).

[0435] method In another embodiment, there is a method for coloring hair, comprising the steps of preparing hair (for example, human hair, a wig, or an article containing hair) and bringing the hair into contact with the hair color composition of the present invention.

[0436] In some embodiments, the hair is human hair. In some embodiments, the hair is damaged hair (for example, as a result of dyeing or bleaching). In some embodiments, the method includes the step of applying a sufficient amount of the hair color composition of the present invention to the hair. In some embodiments, this amount is sufficient to obtain colored hair. In some embodiments, this amount is sufficient to obtain a predetermined hair color. In some embodiments, this amount is sufficient to obtain a stable hair color, where stable is as described herein.

[0437] In another embodiment, there is a method for supplementing a subject with a cosmetic active ingredient, the method comprising the step of supplementing the subject with a cosmetic active ingredient by providing the subject with a composition or article of the present invention.

[0438] In some embodiments, the subject is selected from either a human subject or an animal subject.

[0439] In some embodiments, the method is for skin rejuvenation, skin moisturizing, skin hydration, skin conditioning, wrinkle reduction, prevention of skin irritation, protection from skin contamination, and skin soothing, or any combination thereof, as shown in Figures 14-17 and 18A-B. In some embodiments, the method is as described herein, where the composition or article of the present invention comprises 0.1-20 (w / w)% of the MaSp system protein as described herein.

[0440] In some embodiments, there are methods for improving one or more skin parameters of a subject requiring such improvement, comprising the step of administering a therapeutically effective amount of any one of the compositions or articles disclosed herein to the subject. In other embodiments, the present invention provides methods for treating a subject suffering from a skin-related pathology.

[0441] In some embodiments, one or more skin parameters are selected from facial skin wrinkles (lines / wrinkles), skin aging, skin moisture content, skin elasticity, skin radiance, skin brightness, skin oil content (e.g., reduction correction), and ultraviolet (UV) induced damage.

[0442] In another embodiment, there is a method for reducing or preventing UV-related damage to a subject, comprising the step of applying the sunscreen composition of the present invention to the skin of the subject to reduce or prevent UV-related damage to the subject.

[0443] In another embodiment, there is a method for coloring hair, which includes the step of coloring hair by bringing the hair color composition of the present invention into contact with at least a portion of the hair under appropriate conditions.

[0444] In one embodiment, “skin-related conditions” refer to skin damage caused by extrinsic factors such as exposure to ultraviolet radiation. In one embodiment, skin conditions are caused by irritants. In one embodiment, skin conditions are caused by chemical or any other toxic factor. In one embodiment, skin-related conditions include, but are not limited to, skin thickness, sunburn, erythema, skin irritation, redness, dryness, stinging, peeling and separation of skin, acne-like rashes, skin spots, and uneven skin color tone, infections, and fluid loss, or any combination thereof.

[0445] In the methods disclosed above, the therapeutic composition may be administered by conventional means, but in one embodiment, the composition is administered in a pharmaceutical dosage form, a nutritional dosage form, a nutritional dosage form, or an oral dosage form.

[0446] In one embodiment, the composition of the present invention may be provided to an organism by itself. In one embodiment, the composition of the present invention may be provided to an organism as part of a further pharmaceutical or nutritional supplement composition (e.g., an article) mixed with a pharmaceutically acceptable carrier.

[0447] In one embodiment, “pharmaceutical composition,” “medicinal cosmetic composition,” or “nutritional supplement composition” refers to a formulation of the composition described herein, accompanied by other chemical components such as physiologically appropriate carriers and excipients. The purpose of the pharmaceutical composition, medicinal cosmetic composition, or nutritional supplement composition is to facilitate the administration of the composition to an organism.

[0448] In one embodiment, “combination formulation” specifically defines a “kit of parts” in the sense that the combination partners defined above can be administered independently or in different constant combinations with different amounts of the combination partners, i.e., simultaneously, concurrently, separately, or sequentially. Thus, in some embodiments, the parts of the kit of parts can be administered simultaneously, for example, or adjusted over time at different points in time and at the same or different time intervals with any of the parts of the kit of parts. The ratio of the total amount of the combination partners can be administered in the combination formulation in some embodiments. In one embodiment, the combination formulation can be varied to address, for example, the needs of a subpopulation of patients being treated, or the needs of a single patient, which may be due to the characteristics of the disease, the severity of the disease, age, sex, or weight, which can be easily made by those skilled in the art.

[0449] In one embodiment, the interchangeable terms “physiologically acceptable carrier” and “pharmaceutically acceptable carrier” refer to a carrier or diluent that does not cause significant irritation to mammals and does not inhibit the biological activity and properties of the administered composition. Adjuvants are included in these terms.

[0450] In one embodiment, “excipient” refers to an inert substance added to the composition to further facilitate the administration of the active ingredient. In one embodiment, excipients include calcium carbonate, calcium phosphate, various sugars, and starch seeds, cellulose derivatives, gelatin, vegetable oils, and polyethylene glycol.

[0451] The techniques for the prescription and administration of drugs are found in their entirety in the latest edition of "Remington's Pharmaceutical Sciences," Mack Publishing Co., Easton, PA, which is incorporated herein by reference.

[0452] In one embodiment, suitable routes of administration include, for example, local delivery, skin delivery, transdermal delivery, oral delivery, rectal delivery, transmucosal delivery, nasal delivery, intra-intestinal delivery, or parenteral delivery, and intrathecal injection, direct intraventricular injection, intraperitoneal injection, intranasal injection, or intraocular injection.

[0453] General Provisions Where used herein, the term "approximately" represents ±10%.

[0454] The terms "comprises," "comprising," "includes," and "including," as well as their cognates, all mean "to include, but not to limit."

[0455] The term "~to consist of" means "not limiting, but including ~".

[0456] The term "essentially derived from" means that the composition, method, or structure may include further components, steps, and / or parts only if those further components, steps, and / or parts do not substantially alter the basic and novel characteristics of the claimed composition, method, or structure.

[0457] As used herein, the term “stablely encapsulated” refers to a property of the composition that substantially prevents the release of the active ingredients from the composition. As used herein, the term “substantially prevent” refers to the total amount of active ingredients removed by the first and second tape pieces as measured by a skin tape test (described in the Examples section).

[0458] In some embodiments, the product substantially contains at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 97% by weight, and at least 99% by weight of cosmetic active ingredients. In some embodiments, the product substantially contains at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 97% by weight, and at least 99% by weight of cosmetic active ingredients bonded to the MasP fiber via non-covalent bonds, physical interactions, or both. Non-covalent bonds are well known in the art and include, in particular, hydrogen bonds, pp stacking, van der Waals interactions, and the like.

[0459] The term “exemplary” is used herein to mean “acting as an example, example, or illustration.” All embodiments described as “exemplary” are not necessarily to be construed as being preferable or beneficial to other embodiments, and / or are not to preclude the incorporation of features from other embodiments.

[0460] The term “optionally” is used herein to mean “provided in some embodiments and not in other embodiments.” Any particular embodiment of the present invention may include several “optionally” characteristics, provided that such characteristics do not conflict.

[0461] Where used herein, the singular forms "a," "an," and "the" include the plural form unless the context indicates otherwise. For example, the term "a compound" or "at least one compound" may include multiple compounds (including mixtures thereof).

[0462] definition As used herein, the term "alkyl" refers to an aliphatic hydrocarbon containing linear and branched groups. Preferably, the alkyl group has 1 to 20 carbon atoms, more preferably 1 to 10 or 1 to 6 carbon atoms.

[0463] Furthermore, the term "alkyl," as used herein, encompasses saturated or unsaturated hydrocarbons, and thus the term further encompasses alkenyls and alkynyls.

[0464] The term "alkenyl" refers to an unsaturated alkyl group as defined herein, having at least two carbon atoms and at least one carbon-carbon double bond. Alkenyls may or may not be substituted with one or more substituents, as described herein.

[0465] The term "alkynyl," as defined herein, is an unsaturated alkyl having at least two carbon atoms and at least one carbon-carbon triple bond. Alkynnyls may or may not be substituted with one or more substituents, as described herein.

[0466] The term "cycloalkyl" refers to a monocyclic or fused ring (i.e., a ring sharing pairs of adjacent carbon atoms) in which one or more rings do not have a fully conjugated π-electron system. Cycloalkyl groups may or may not be substituted, as shown herein.

[0467] The term "aryl" refers to a monocyclic or polycyclic group of all carbon atoms having a fully conjugated π-electron system (i.e., a ring sharing pairs of adjacent carbon atoms). Aryl groups may or may not be substituted, as shown herein.

[0468] The term "alkoxy" refers to O-alkyl groups and -O-cycloalkyl groups as defined herein.

[0469] The term "aryloxy" refers to the -O-aryl as defined herein.

[0470] In the general formulas herein, alkyl, cycloalkyl, and aryl groups may each be substituted with one or more substituents, so that each substituent can independently be, depending on the substituted group and its position in the molecule, for example, a halide, alkyl, alkoxy, cycloalkyl, nitro, amino, hydroxyl, thiol, thioalkoxy, carboxy, amide, aryl, and aryloxy. Further substituents may also be considered.

[0471] The terms "halogen," "halogen," or "halo" refer to fluorine, chlorine, bromine, or iodine.

[0472] The term "haloalkyl" refers to an alkyl group as defined herein, which is further substituted with one or more halides.

[0473] The term "substituted" or "substituent" refers to one, two, three, four, or five substituents, where each substituent independently is (C0-C6)alkyl-aryl, (C0-C6)alkyl-heteroaryl, (C0-C6)alkyl-(C3-C8)cycloalkyl, optionally substituted C3-C8 heterocyclyl, halogen, NO2, -CN, -OH, -CONH2, -CONR2, -CNNR2, -CSNR2, -CONH-OH, -CONH-NH2, -NHCOR, -NHCSR, -NHCNR, -NC(=O)OR, -NC(=O)NR, -NC(=S)OR, -NC(=S)NR, SO2R, SOR, -SR, SO2OR, SO2N(R)2, -NHNR2, -NNR, C1 -C6 haloalkyl, optionally substituted C1-C6 alkyl, -NH2, -NH(C1-C6 alkyl), -N(C1-C6 alkyl)2, C1-C6 alkoxy, C1-C6 haloalkoxy, hydroxy(C1-C6 alkyl), hydroxy(C1-C6 alkoxy), alkoxy(C1-C6 alkyl), alkoxy(C1-C6 alkoxy), C1-C6 alkylNR2, C1-C6 alkyl-SR, -CONH(C1-C6 alkyl), -CON(C1-C6 alkyl)2, -CO2H, -CO2R, -OCOR, -OCOR, -OC(=O)OR, -OC(=O)NR, -OC(=S)OR, -OC(=S)NR (including any combination thereof).

[0474] The term "haloalkoxy" refers to an alkoxy group as defined herein that is further substituted with one or more halides.

[0475] The term "hydroxyl" or "hydroxy" refers to the -OH group.

[0476] The terms "mercapto" or "thiol" refer to the -SH group.

[0477] The term "thioalkoxy" refers to -S-alkyl and -S-cycloalkyl groups as defined herein.

[0478] The terms "thioaryloxy" both refer to the -S-aryl group and the -S-heteroaryl group as defined herein.

[0479] The term "amino" refers to the -NR'R'' group, where R' and R'' are as defined herein.

[0480] The term "heterocyclyl" refers to a monocyclic or fused ring group containing one or more atoms, such as nitrogen, oxygen, and sulfur, in its ring. This ring may also contain one or more double bonds. However, this ring does not have a fully conjugated π-electron system. Typical examples include piperidine, piperazine, tetrahydrofuran, tetrahydropyran, and morpholino.

[0481] The terms "carboxy" or "carboxylate" represent the -C(O)OR' group (wherein R' is a hydrogen, alkyl, cycloalkyl, alkenyl, aryl, heteroaryl (bonded via a ring carbon), or heterocyclyl (bonded via a ring carbon) as defined herein).

[0482] The term "carbonyl" represents the -C(O)R' group (wherein R' is as defined above in this specification).

[0483] Alternatively, the above terms include their thio derivatives (thiocarboxy and thiocarbonyl).

[0484] The term "thiocarbonyl" represents the -C(S)R' group (wherein R' is as defined above in this specification).

[0485] The "thiocarboxyl" group represents a -C(S)OR' group (wherein R' is as defined herein).

[0486] The "sulfinyl" group represents the -S(O)R' group (wherein R' is as defined herein).

[0487] The "sulfonyl" or "sulfonate" group represents the -S(O)2R' group (wherein R' is as defined herein).

[0488] The "carbamyl" or "carbamate" group represents the -OC(O)NR'R'' group (wherein R' is as defined herein, and R'' is as defined by R').

[0489] The "nitro" group represents the -NO2 group.

[0490] The term "amide," as used herein, encompasses both C-amides and N-amides.

[0491] The term "C-amide" refers to the -C(O)NR'R'' terminal group or the -C(O)NR'- bond group (these terms are defined herein as above, and R' and R'' are as defined herein).

[0492] The term "N-amide" refers to the -NR''C(O)R' terminal group or the -NR'C(O)- bond group (these terms are defined herein as above, and R' and R'' are as defined herein).

[0493] The term "carboxylic acid derivative," as used herein, includes carboxy, amide, carbonyl, anhydride, carbonate ester, and carbamate.

[0494] The "cyano" or "nitrile" group represents the -CN group.

[0495] The terms "azo" or "diazo" refer to an N=NR' terminal group or an N=N bond group (as defined herein above, where R' is as defined herein).

[0496] The term "guanidine" refers to the -R'NC(N)NR''R''' terminal group or the -R'NC(N)NR''- bond group (these terms are defined herein as above, and R', R'', and R''' are as defined herein).

[0497] As used herein, the term "azid" refers to the -N3 group.

[0498] The term "sulfonamide" refers to the -S(O)2NR'R'' group, where R' and R'' are as defined herein.

[0499] The term "phosphonyl" or "phosphonate" refers to a -OP(O)-(OR')2 group, where R' is as defined herein.

[0500] The term "phosphenyl" refers to the -PR'R'' group, where R' and R'' are as defined herein above.

[0501] The term "alkylaryl" refers to an alkyl group as defined herein, substituted with an aryl group as described herein. An exemplary alkylaryl is benzyl.

[0502] The term "heteroaryl" refers to a monocyclic group (e.g., a C5-C6 heteroaryl ring) or a fused ring group (i.e., a ring sharing an adjacent pair of atoms) having a mitotic and even fully conjugated π-electron system with one or more atoms, such as nitrogen, oxygen, and sulfur, in the ring. In some embodiments, the terms "heteroaryl" and "C5-C6 heteroaryl" are used interchangeably herein. Examples of heteroaryl groups, but not limited to, include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, isoquinoline, and purine. Heteroaryl groups may or may not be substituted with one or more substituents as defined above herein. Typical examples include thiadiazole, pyridine, pyrrole, oxazole, indole, and purine.

[0503] Where used herein, the terms “halo” and “halogen” are interchangeable herein to refer to an atom of a halogen which is fluorine, chlorine, bromine, or iodine, and also herein to refer to fluoride, chloride, bromide, and iodide.

[0504] The term "haloalkyl" refers to an alkyl group as defined above, which is further substituted with one or more halides.

[0505] Throughout this application, various embodiments of the present invention may be presented in a range form. It should be understood that this range form is for convenience and brevity only and should not be interpreted as an invariant limitation within the scope of the present invention. Therefore, a range description is considered to have all the prospective subranges and individual numbers within those ranges that are specifically disclosed. For example, a range description such as 1-6 is considered to have specifically disclosed subranges, such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., and individual numbers within those ranges, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0506] Regardless of when it is described herein, a mathematical range is meant to include all the numbers (fractions or integers) described within that range. The “rangings” between the first and second notation numbers and the “ranges from” the first notation number to the second notation number are used interchangeably herein and mean to include the first and second notation numbers, as well as all fractions and integers between them.

[0507] As used herein, the term “method” means, but does not limit, any method, means, techniques, and techniques for accomplishing a given task, including, but is not limited to, methods, means, techniques, and techniques that are known to practitioners in the fields of chemistry, pharmacology, biology, biochemistry, and medicine, or that can be readily developed from methods, means, techniques, and techniques known to practitioners in the fields of chemistry, pharmacology, biology, biochemistry, and medicine.

[0508] As used herein, the term “treating” includes inhibiting, substantially inhibiting, delaying, or reversing the progression of a condition, substantially relieving the clinical or aesthetic symptoms of a condition, or substantially preventing the appearance of the clinical or aesthetic symptoms of a condition.

[0509] Certain aspects of the present invention are described in the context of separate embodiments for clarity, but it should be understood that they may also be provided in combination in a single embodiment. Conversely, various features of the present invention are described in the context of a single embodiment for brevity, but they may also be provided separately, in any suitable subordinate combination, or as appropriate in any other described embodiment of the present invention. Features described in the context of various embodiments should not be considered essential features of that embodiment unless that embodiment would be invalid without that component.

[0510] The various embodiments and aspects of the present invention described above and claimed in the following claims section are experimentally supported in the following examples.

[0511] Examples The following examples are mentioned here, illustrating some embodiments of the present invention in a non-limiting manner, along with the above description.

[0512] Skin tape test Tape removal is a simple and efficient method for evaluating the quality and efficacy of cosmetic and dermatological formulations. Following topical application and penetration of the formulation, the stratum corneum cell layer is continuously removed from the same skin area using an adhesive film. Tape is applied and then removed from the skin surface to which the formulation was applied every 10 minutes. Each tape piece was analyzed by FTIR technology. The tape's cellophane polymer corresponds to 1450 cm². -1 The peaks were normalized to the same height.

[0513] Example 1 Derivatized MaSp-based fibers

[0514] The amination of MaSp fibers was carried out as follows.

[0515] An aqueous dispersant containing MaSp fibers with an anionic surfactant (as used herein as "SVX") was centrifuged and redispersed in deionized (DI) water. Furthermore, the MaSp fibers were substantially dried by a well-established method and redispersed in DI water to obtain a MaSp suspension.

[0516] After preparing an aqueous solution of 2-(4-aminophenyl)ethylamine (APEA) (1-20 w / w%), it was acidified with HCl (1M).

[0517] 2-10 molar excess NaNO2 was added to a 2-(4-aminophenyl)ethylamine solution, and the mixture was kept at a temperature of 1-20°C for 10-60 minutes to obtain a diazotized solution. Next, the diazotized solution was added dropwise to the MaSp suspension while cooling. The resulting mixture was stirred until the reaction was complete.

[0518] Next, the supernatant was discarded, the remaining derivatized MaSp fibers were thoroughly washed with DI water, and then the amination fibers were dried.

[0519] The modification efficiency (yield) was determined by calculating the amount of unreacted APEA in the reaction mixture. This calculation was performed by determining the UV adsorption of APEA (via UV spectrophotometry). Up to 60% tyrosine diazotization was observed.

[0520] The conjugation of polyglutaraldehyde (PGA) and amination-modified MaSp fibers was performed as follows. Preparation of polyglutaraldehyde (average MW: 500-2000 or approximately 1000 Da)

[0521] 20 ml of a 25% glutaraldehyde aqueous solution was added to an aqueous solution of K2CO3 (1M) and heated at 50°C for 2 hours. Next, it was cooled to RT (room temperature, 20-25°C) and the pH was set to 7 using 37% HCl. This was then centrifuged at 7000 rpm for 10 minutes and the liquid was diluted with acetone to 10 times its volume. The K2CO3 powder was filtered and the acetone was vaporized. The PGA aqueous solution was freeze-dried and stored at -20°C.

[0522] Amination of MaSp fibers was added to an aqueous buffer containing 1-10 ml of polyglutaraldehyde (PGA) solution (0.01-2 M concentration). The resulting suspension was then cooled to RT and the pH was neutralized using HCl (37%). This reaction was continued overnight at 1-10°C with stirring to obtain the desired product: SVX-PGA.

[0523] The inventors have succeeded in synthesizing amination-MaSp fibers bonded to PGA (where PGA is further bonded to a metal oxide chelate group (salicylic acid), as shown in Formula 4).

[0524] Conjugation of metal oxide chelating groups (salicylic acid, SA) to polyglutaraldehyde (PGA) The inventors have succeeded in synthesizing PGA-derivativeized MaSp fibers modified with a metal oxide chelating agent (succinic acid), as shown in Formula 4.

[0525] The modified MaSp fiber (SVX-PGA-SA) of formula 4 was synthesized by reacting SVX-PGA (prepared by the method of Example 1) with 4-aminosalicylic acid as follows:

[0526] An aqueous dispersion (pH 10.5) containing 300 mg of SVX-PGA was mixed with 150 mg (excess) of 4-aminosalicylic acid at 20-40°C for 1-10 hours. The reaction mixture changed color to orange. Next, the reaction mixture was centrifuged, and the solid SVX-PGA-SA was washed several times to remove all unreacted aminosalicylic acid.

[0527] Complex formation of titania particles by MaSp-based fibers modified with PGA-SA As described below, titania particles (particle size 300-500 nm) were complexed with SVX-PGA-SA to obtain the composite TiO2-SVX-PGA-SA.

[0528] An aqueous dispersion (pH 3.5) containing 200 mg of SVX-PGA-SA was mixed with 200 mg of titanium dioxide at 40°C for 10 hours. The color of the reaction mixture changed to dark red. Next, the reaction mixture was centrifuged, and the solid TiO2-SVX-PGA-SA was washed several times to remove all unreacted substances.

[0529] SEM images of the derivatized MaSp fibers are shown in Figures 24A and 24B, indicating the significant porosity of the derivatized MaSp fibers (e.g., at least 10 m). 2This is represented by the BET surface area (defined by the BET surface area per g).

[0530] Figure 23 shows an exemplary graph representing the zeta potential of the derivatized fiber. As shown in Figure 23, the zeta potential of the derivatized fiber of the present invention is modified compared to the fiber in its original state. Furthermore, Figure 23 shows that the zeta potential is predetermined by the chemical modification (functional portion) of the derivatized fiber.

[0531] Example 2 Hair color composition The inventors have successfully implemented hair color compositions (for example, the color compositions described herein) containing various derivatized porous MaSp fibers. Some of these hair color compositions resulted in a uniform and stable coating of hair after contact with hair (e.g., human hair). Exemplary hair color compositions that successfully implemented hair coating include amination-MaSp fibers (chemically modified with 4-(2-aminoethyl)aniline (APEA); 3-aminopropyl (amonipropyl)triethoxysilane (APTES) or PEI). Furthermore, several dyes (cationic and anionic dyes) were implemented in the hair coating, resulting in colored hair. The colored hair formed after application of the hair color compositions described herein retained its color even after thorough washing.

[0532] Furthermore, the inventors utilized various MaSp-based fibers for hair color compositions. Stable hair coating was obtained by using amination-MaSp-based proteins and amination-mutant MaSp-based proteins.

[0533] Furthermore, as shown in Figure 25, applying the hair coating composition to human hair under acidic conditions (pH below the amine's pKa, e.g., pH below 8, below 7, below 6, below 5, below 4) resulted in a sufficient coating layer. In contrast, when the hair coating composition was applied to human hair under basic conditions (pH above 10), the fibers did not adhere to the hair, and therefore no coating layer was obtained (Figure 25B).

[0534] The inventors have successfully developed hair coating compositions containing various derivatized fibers of the present invention (e.g., those containing cationic functional groups), such as derivatized MaSp fibers with PEI modification, amino modification (via APEA), and aminosilane modification (via APTES). When these derivatized fibers are applied at an acidic pH, a stable coating layer is obtained on human hair, as illustrated in Figures 25-27.

[0535] Example 3 Sunscreen composition The composite of the present invention (synthesized as described in Example 1), containing titanium dioxide particles having a particle size greater than 300 nm, exhibited significantly improved dispersibility in aqueous solutions and / or organic solvents compared to the original titania particles. Aqueous dispersions containing titanium dioxide nanoparticles bound (complexed) via salicylates (represented by formula 4, for example) bonded to PGA-derivativeized MaSp fibers exhibited superior sunscreen effect compared to the original titanium dioxide nanoparticles. Furthermore, the composite containing titanium dioxide particles bonded to salicylate-derivativeized MaSp fibers exhibited excellent dispersibility (e.g., able to form a stable dispersion) (where the w / w ratio of titanium dioxide particles to the derivatized MaSp fibers is approximately 1:1).

[0536] The aforementioned complex was used to reduce UV exposure (for example, to human skin).

[0537] Example 4 Hyaluronic acid filling and release SVX (Spider silk fiber) or spider silk fibers expressed with bacteria (SVX-E) were washed twice with ethanol (as described above in this specification) and then with water. 10 mg of hyaluronic acid (HA) was added to 10 mg of SVX dispersed in 1–20 mL of water. The pH was adjusted with HCl or phosphate buffer, and water was added to achieve the desired volume. The mixture was shaken and centrifuged. The supernatant was discarded, and the small pellet samples were dried on a glass slide to yield HA+SVX-E or HA+SVX pellets. These pellets were then tested by FTIR (Nicolet iS5 FTIR Spectrometer, Thermo Fisher Scientific). The remaining pellets were resuspended in water, and the suspension was shaken at 25°C and 200 rpm for 1–30 minutes. Samples were analyzed by FTIR for each pellet, and the percentage of HA in the total dry weight was calculated by dividing the peak intensity specific to HA by the peak intensity specific to the polymer (Table 1). These results confirmed the properties of MaSp-based fibers (e.g., SVX or SVX-E) that stably encapsulate further compounds (e.g., HA) (where the w / w ratio of the encapsulated compound to the fiber (e.g., SVX or SVX-E) is approximately 1:1). [Table 1]

[0538] The release profiles of HA from SVX, SVX-E, silk, and cellulose are shown in Figure 20. Figure 20 shows sustained release from SVX and SVX-E compared to rapid release from the transitions of silk and cellulose.

[0539] Example 5 Filling and release of retinyl acetate and glycerol from SVX-E fibers Spider silk fibers expressed in bacteria (SVX-E) were pretreated as described above. The pretreated SVX-E was then combined with retinyl acetate or glycerol to form pellets according to the method described in Example 1. The release of the active ingredient (retinyl acetate or glycerol) was estimated by FTIR according to the method described in Example 1. Graphs showing the release profiles of the active ingredient are shown in Figures 22A-B.

[0540] Example 6 Filling and release of α-hydroxycarboxylic acids and HA To evaluate the release of HA and α-hydroxycarboxylic acids (e.g., glycolic acid, GA, and lactic acid, LA) from SVX-E formulations, the inventors prepared the following exemplary liquid compositions according to the protocol described herein. The compositions tested and negative controls are summarized in Table 2. [Table 2]

[0541] The compositions tested and negative controls were prepared as follows: Control 1: Control 1 (10 ml) was prepared by dissolving 0.5 g of film-forming agent (pullulan) in 9.3 g of water, and then adding 0.2 g of lactic acid.

[0542] Control 2: 10 ml of Control 2 was prepared by dissolving 0.5 g of film-forming agent (pullulan) in 8.0 g of water, and then adding 1.5 g of glycolic acid solution (33%). Control 3: 10 ml of Control 3 was prepared by dissolving 0.5 g of film-forming agent (pullulan) in 9.5 g of HA solution (1%). The LA+SVX-E sample was prepared by mixing 0.5 g of film-forming agent (pullulan), 1.0 g of SVX-E, 0.2 g of LA, and 8.3 g of water. The GA+SVX-E sample was prepared by mixing 0.5 g of film-forming agent (pullulan), 1.0 g of SVX-E, 1.5 g of GA solution (33%), and 7.0 g of water. The HA+SVX-E sample was prepared by mixing 0.5 g of film-forming agent (pullulan), 1.0 g of SVX-E, and 8.5 g of HA solution (1%).

[0543] As shown in Figure 21, the release rate of cosmetic active ingredients (e.g., LA, GA, and HA) in the SVX-E fiber-based liquid composition was slower compared to the control. As illustrated herein, the SVX-E fiber-based liquid composition allows for extended retention time of various cosmetic ingredients on the skin surface. In some embodiments, the release rate of compounds is predetermined by the size and molecular weight of each compound (i.e., cosmetic ingredient).

[0544] Furthermore, it was found that SVX-E fiber-based liquid compositions with a film-forming agent concentration exceeding 10 (w / w)% were too viscous and had a non-homogeneous texture, making them unsuitable for cosmetic application. Additionally, SVX-E fiber-based liquid compositions with a film-forming agent concentration of less than 1 (w / w)% were characterized by insufficient viscosity and were therefore unsuitable for cosmetic application. In some embodiments, liquid compositions containing 1 to 15 (w / w)% film-forming agent are characterized by a viscosity suitable for cosmetic application. In some embodiments, liquid compositions containing 1 to 15 (w / w)% film-forming agent are capable of forming a film. In some embodiments, a film-forming agent at a concentration of 1 to 15 (w / w)% in the liquid composition provides sufficient flexibility. Cosmetic compositions with sufficient flexibility can be applied to the target skin (for example, by spreading).

[0545] Data obtained by the inventors showed that 10% SVX-E of the total weight of the liquid composition was necessary to obtain a significant reduction in wrinkle depth and to provide significant skin contouring. Furthermore, it was found that liquid compositions reinforced with 1-20 (preferably 10)(w / w)% SVX-E fibers containing cosmetic ingredients (e.g., GA, LA, and / or HA) were suitable for supplementing the target skin with cosmetic ingredients. In some embodiments, the amount of cosmetic ingredients is sufficient to induce a significant medicinal cosmetic effect (e.g., the effect described in the Methods section).

[0546] Although the present invention has been described in conjunction with its specific embodiments, it is obvious that many alternatives, modifications, and variations will be apparent to those skilled in the art. Therefore, it is intended that all such alternatives, modifications, and variations be included in the spirit and scope of the appended claims.

[0547] All publications, patents, and patent applications referenced herein are incorporated herein by reference to the same extent as if each individual publication, patent, or patent application were specifically and individually described herein as being incorporated herein by reference. Furthermore, all references or identifications in this application should not be construed as an acknowledgment that such references are available as prior art to the present invention. Section headings, insofar as they are used, should not necessarily be construed as limitations.

Claims

1. A medicated cosmetic composition comprising an effective amount on a medicated cosmetic surface of a complex containing derivatized porous MaSp (major amplifier spirulin protein) fibers bonded to metal oxide particles, The derivatized porous MaSp fiber comprises at least 10 m ２ Characterized by a BET surface area of ​​ / g, The derivatized porous MaSp fiber comprises a polymer covalently bonded to the tyrosine side chain of the derivatized porous MaSp fiber, wherein the covalent bond is formed via a diazo bond and / or a silyl group, or a combination thereof. The polymer comprises one or more metal oxide chelate groups, The metal oxide particles are bonded to the derivatized porous MaSp fiber via the metal oxide chelate group. A medicated cosmetic composition.

2. The medicinal cosmetic composition according to claim 1, further comprising a cosmetically acceptable carrier.

3. A medicated cosmetic composition according to claim 1 or 2, characterized as a sunscreen composition.

4. The medicated cosmetic composition according to claim 1, wherein the effective amount on the medicated cosmetic is 10 (w / w)% to 50 (w / w)% of the complex in the composition.

5. The medicated cosmetic composition according to claim 2, characterized as a hair color composition.

6. The medicinal cosmetic composition according to claim 1, wherein the metal oxide particles are selected from titania, zirconia, silica, or any combination thereof.

7. The medicinal cosmetic composition according to claim 1, wherein the metal oxide particles are characterized by having a particle size of 10 to 5,000 nm.

8. The medicinal cosmetic composition according to claim 1, wherein the w / w ratio of the derivatized porous MaSp fibers in the composition to the metal oxide particles is 0.01 to 100.

9. The medicated cosmetic composition according to claim 1, wherein the polymer comprises polyglutaraldehyde (PGA), and the w / w ratio of the polymer to the derivatized porous MaSp fiber is 0.001 to 5.

10. The medicinal cosmetic composition according to any one of claims 1 to 9, wherein the derivatized porous MaSp fiber is in the form of particles having an average particle size in the range of 0.5 μm to 1.5 μm.

11. The medicinal cosmetic composition according to claim 10, wherein the derivatized porous MaSp fiber is a synthetic protein, and the particles comprise a plurality of nanofibers characterized by a diameter of 4 to 16 nm and a plurality of pores.

12. The aforementioned derivatized porous MaSp fiber has a decomposition temperature (T) of 280°C to 350°C, determined by differential scanning calorimetry (DSC). ｄ The medicinal cosmetic composition according to claim 1, characterized by the following:

13. The derivatized porous MaSp fiber has a glass transition temperature (T) of 200°C to 250°C determined by DSC. ｇ The medicinal cosmetic composition according to claim 1, characterized by the following:

14. The derivatized porous MaSp-based fiber has the amino acid sequence shown by Formula 10: (X １ ), Ｚ X ２ GPGGYGPX ３ X ４ X ５ GPX ６ GX ７ GGX ８ GPGGPGX ９ X １０ wherein, X １ is independently A or G at each position, Z is an integer of 5 to 30, X ２ is S or G, X ３ is G or E, X ４ is G, S, or N, X ５ is Q or Y, X ６ is G or S, X ７ is P or R, X ８ is Y or Q, X ９ is G or S, X １０ is S or G), and the pharmaceutical cosmetic composition according to claim 1, which contains a repeating region.

15. A medicated cosmetic composition according to claim 1, for use in reducing or preventing UV-related damage to a target.

Images