Tinted low concentration fullerene, graphene, and nanotube skin care compositions

Abstract

Provided herein are compositions, systems, kits, and methods for using various low concentrations of functionalized fullerenes (e.g., polyhydroxy fullerenes), functionalzied graphene (e.g., graphene oxide), and / or functionalized carbon nanotubes (e.g., carboxylated multiwalled carbon nanotubes), to generate tinted skin care compositions, such as sunscreens and cosmetics, that a user can apply to generally match their skin tone. In certain embodiments, the compositions, kits, and systems herein comprise a dermatologically acceptable carrier (e.g., that is white or light in color prior to being in the composition) and a functionalized fullerene compound, functionalized graphene, and / or functionalized carbon nanotubes, for tinting present at a concentration of about 0.1% (e.g., for very light tan) to about 3.0% (e.g., for very dark brown). In certain embodiments, the compositions herein are present in a container, such as a sunscreen container or makeup container.

Description

[0001]Attorney Docket No.: CCF-41807.601 TINTED LOW CONCENTRATION FULLERENE, GRAPHENE, AND NANOTUBE SKIN CARE COMPOSITIONS The present application claims priority to U.S. provisional application serial number 63 / 621,247, filed January 16, 2024, which is herein incorporated by reference in its entirety. This invention was made with government support under W81XH-22-1-1041 awarded by the Department of Defense. The government has certain rights in the invention. FIELD Provided herein are compositions, systems, kits, and methods for using various low concentrations of functionalized fullerenes (e.g., polyhydroxy fullerenes), functionalzied graphene (e.g., graphene oxide), and / or functionalized carbon nanotubes (e.g., carboxylated multiwalled carbon nanotubes), to generate tinted skin care compositions, such as sunscreens and cosmetics, that a user can apply to generally match their skin tone. In certain embodiments, the compositions, kits, and systems herein comprise a dermatologically acceptable carrier (e.g., that is white or light in color prior to being in the composition) and a functionalized fullerene compound, functionalized graphene, and / or functionalized carbon nanotubes, for tinting present at a concentration of about 0.1% (e.g., for very light tan) to about 3.0% (e.g., for very dark brown). In certain embodiments, the compositions herein are present in a container, such as a sunscreen container or makeup container. BACKGROUND Every year, over one million new cases of skin cancer are diagnosed in the U.S., outnumbering the total number of all other cancer diagnoses combined, imposing an annual economic burden of $8.1 billion for skin cancer treatment. Exposure to UV radiation is the most common, and also the most preventable, cause of skin cancers. Skin damage with UV exposure occurs through at least two mechanisms: (i) direct damage to DNA, mainly from UVB (280-320 nm), and (ii) production of free radicals from UVA (320-400 nm), which destroy intracellular components including DNA, membranes, and proteins. Sunscreens are the first step in skin cancer prevention. Sunscreen agents include both organic sunscreens and inorganic sunscreens. Inorganic sunscreens include inorganic particles which provide protection to the skin by directly blocking solar radiation. Examples of inorganic sunscreens include zinc oxide and titanium dioxide. However, a problem with Attorney Docket No.: CCF-41807.601 inorganic sunscreens is that they give the skin an unnatural whiteness when applied at effective concentrations. SUMMARY Provided herein are compositions, systems, kits, and methods for using various low concentrations of functionalized fullerenes (e.g., polyhydroxy fullerenes), functionalzied graphene (e.g., graphene oxide), and / or functionalized carbon nanotubes (e.g., carboxylated multiwalled carbon nanotubes), to generate tinted skin care compositions, such as sunscreens and cosmetics, that a user can apply to generally match their skin tone. In certain embodiments, the compositions, kits, and systems herein comprise a dermatologically acceptable carrier (e.g., that is white or light in color prior to being in the composition) and a functionalized fullerene compound, functionalized graphene, and / or functionalized carbon nanotubes, for tinting present at a concentration of about 0.1% (e.g., for very light tan) to about 3.0% (e.g., for very dark brown). In certain embodiments, the compositions herein are present in a container, such as a sunscreen container or makeup container. In some embodiments, provided herein are compositions comprising: a) a dermatologically acceptable carrier; and b) at least one compound selected from: a functionalized fullerene compound, functionalized graphene, and functionalized carbon nanotubes, wherein the functionalized fullerene compound, if present, is present in the composition at a concentration of about 0.1% to 3.0%, wherein the functionalized graphene, if present, is present in the composition at a concentration of about 0.01% to 1.0% by weight, wherein the functionalized carbon nanotubes, if present, are present in the composition at a concentration of about 0.01% to 1.0% by weight, wherein optionally the composition has a gradual darkening shade of brown color from very light tan to very dark brown depending on: i) the concentration of the functionalized fullerene compound present, ii) concentration of the functionalized graphene present, or iii) concentration of the functionalized carbon nanotubes present, wherein a concentration of: i) about 0.1% of the functionalized fullerene compound, ii) about 0.01% by weight of the functionalized graphene, or iii) about 0.01% of the functionalized carbon nanotubes provides the very light tan color to the composition, and wherein a concentration of: i) about 3.0% of the functionalized fullerene compound, ii) about 1.0% by weight of the functionalized graphene, or iii) about 1.0% by weight of the functionalized carbon nanotubes provides the very dark brown color. In certain embodiments, the dermatologically acceptable carrier is white or light in color prior to being in the composition and / or wherein the composition would have a generally white color if the at least one compound were not present. In other embodiments, Attorney Docket No.: CCF-41807.601 the concentration of the functionalized fullerene compound is selected from: about 0.25%, about 0.5%, about 0.75%, about 1.0%, about 1.25%, about 1.5%, about 1.75%, about 2.0%, about 2.25%, about 2.5%, about 2.75%, and about 3.0%; and / or wherein the concentration of the functionalized graphene or functionalized carbon nanotubes is selected from: about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 0.75%, or about 1.0%. In further embodiments, the composition further comprises titanium dioxide and / or zinc oxide. In other embodiments, the composition comprises the titanium dioxide, and wherein the titanium dioxide is present in the composition at a concentration between 0.1% and 20% or between 0.1% and 10%. In further embodiments, the titanium dioxide is present in the composition at a concentration of about 7.5%. In additional embodiments, the composition comprises the zinc oxide, and wherein the zinc oxide is present in the composition at a concentration between 0.1% and 20% or between 0.1% and 10%. In other embodiments, the zinc oxide is present in the composition at a concentration of about 7.5%. In other embodiments, the composition comprises the zinc oxide and the titanium dioxide, and wherein the zinc oxide is present in the composition at a concentration between 0.1% and 20% or between 0.1% and 10%, and wherein the titanium dioxide is present in the composition at a concentration between 0.1% and 20%, or between 0.1% and 10%. In further embodiments, the zinc oxide is present in the composition at a concentration of about 7.5%, and wherein the titanium dioxide is present in the composition at a concentration of about 7.5%. In some embodiments, the compositions further comprise a sun protection factor (SPF) agent and / or a ultraviolet A protection factor (PFA) agent. In other embodiments the the SPF or PFA agent is selected from the group consisting of: TiO2, ZnO, Avobenzone, Oxybenzone, Octocrylene, Octisalate, Homosalate, Octinoxate, Cinoxate, Dioxybenzone, Ensulizole, Meradimate, Padimate O, Sulisobenzone, PABA, Trolamine salicylate, Tinosorb S, Tinosorb A2B, Tinosorb M, Mexoryl SX, Ecamsule, Mexoryl XL, Uvinul A Plus, Neo Heliopan AP, Uvinul T 150, Amiloxate, Polysilicone-15, Iscotrizinol, Enzacamene, Triasorb, Camphor Benzalkonium Methosulfate, Benzophenone-3, or any combination thereof. In additonal embodiments, the SPF or PFA agent is: i) ZnO, ii) TiO2 and ZnO, iii) Avobenzone, or iv) ecamsule and / or ensulizole. In some embodiments, the fullerene compound is selected from: a hydroxy fullerene, a carboxy fullerene, a polyamino fullerene, pegylated fullerene, a fullerene hydride, and a halogenated fullerene, and / or the graphene comprises graphene oxide, reduced graphene oxide, and aminate graphene and / or wherein the caron nanotubes comprise hydroxylated nanotubes, aminated nanotubes, and carboxylated multiwalled carbon nanotubes. In other Attorney Docket No.: CCF-41807.601 embodiments, the composition is free of a brown or tan colorant except for the at least one compound. In certain embodiments, the fullerene compound is present and is a hydroxy fullerene according to the formula: C2n(OH)t(NH2)v(COOH)w(COOM)xOyMz, wherein: i) M is an alkali metal, alkaline earth metal, transition metal, post-transition metal, or lanthanide, ii) n is a number ranging from 10 to 270, iii) t is number ranging from 0 to 60, iv) v is a number ranging from 0 to 60, v) w is a number ranging from 0 to 60, vi) x is a numbering ranging from 0 to 60, vii) y is a number ranging from 0 to 30, viii) z is a number ranging from 0 to 30, and wherein (t+y)>z and t>y. In particular embodiments, wherein (t+y)>z and t>y; and / or wherein n is 25–42; and / or wherein t is 4-44; and / or wherein y is 1- 44; and / or wherein z is 1-20. In other embodiments, the fullerene compound is present and is selected from the group consisting of: C60(OH)9O7Na6; C60(OH)11O8Na5; C60(OH)11O12Na8; C60(OH)11O20Na10K6; C60(OH)6O4Na4; C60(OH)20O8Na4; C60(OH)10O13Na6; C60(OH)4O14Na17; C60(OH)13O4Na3; C60O13Na14; Gd@C82(OH)15O12Na5; Gd3N@C80(OH)13O9Na6; C60(OH)11O8S8Na5; C60(OH)11(SH)5O8Na5; C60C12N4H24; C60C12N6H30O12; and C60(OH)12O13Na13. In some embodiments, the fullerence compound is selected from the following, including mixtures of any 2, 3, or 4 thereof: i) C60(OH)17O16Na23; ii) C60(OH)10O12Na13; iii) C60(OH)13O9Na6; and / or C60(OH)12O12Na10. In other embodiments, the dermatologically acceptable carrier comprises a sunscreen lotion, cream, or makeup. In further embodiments, the dermatologically acceptable carrier comprises an emulsion selected from: a single emulsion, a double emulsion, or multiple emulsion. In other embodiments, the emulsion comprises a hydrophilic phase and a hydrophobic phase. In some embodiments, the hydrophobic phase comprises oil. In other embodiments, the the oil is selected from the group consisting of: Red Raspberry Seed Oil, Carrot Seed Oil, Wheat Germ Oil, Almond Oil, Avocado Oil, Coconut Oil, Hemp Seed Oil, Jojoba Oil, Macadamia Oil, Olive Oil, Sesame Seed Oil, Shea Butter, a plant seed oil, and a synthetic oil, and any combination thereof. In some embodiments, the dermatologically acceptable carrier comprises a cosmetic cream or lotion. In further embodiments, the dermatologically acceptable carrier comprises at least one of the following: Water, Cocoyl caprylate, Stearyl / octyldodecyl citrate crosspolymer, Polyhydroxystearic acid, Cetearyl olivate / sorbitan olivate, Benzyl alcohol-dehydroacetic acid, Cetearyl alcohol, Polyacrylate crosspolymer-6, xanthan gum, tetrasodium and EDTA. In other embodiments, at least 25% or at least 50% of the composition comprises water by weight. In further embodiments, the fullerene compound is present and is selected Attorney Docket No.: CCF-41807.601 from the following: C20, C24, C34, C36, C40, C44, C60, C72, C80, C82, C84, C96, C180, C240, C260, C320 and C540. In certain embodiments, the fullerene compound is present and has a generally symmetrical spherical structure. In particular embodiments, the fullerene compound is present and has a cage structure without internal atoms or is an endohedral fullerene. In some embodiments, provided herein are compositions comprising: a) a dermatologically acceptable carrier (e.g., which may be a sunscreen or cosmetic product, or the carrier base for such products); and b) a functionalized fullerene compound (e.g., polyhydroxy fullerene), graphene (e.g., graphene oxide), and / or carbon nanotubes (e.g., carboxylated multiwalled carbon nanotubes), wherein the functionalized fullerene compound is present in the composition at a concentration of about 0.1% to about 3.0% (e.g., about 0.1%...0.3% … 0.5% … 0.7% … 0.9% … 1.1% … 1.3% … 1.5% … 1.7% … 1.9% … 2.1% … 2.3% … 2.5% … 2.7% … 2.9% … or 3.0%), wherein the composition has a gradual darkening shade of brown color from very light tan to very dark brown depending on the concentration of the functionalized fullerene compound present, wherein a concentration of 0.1% of the functionalized fullerene compound providing the very light tan color to the composition, and wherein a concentration of about 3.0% of the functionalized fullerene compound providing the very dark brown (or dark yellow) color (and there is a darkening gradient of brown tint as one goes from about 0.1% to 3.0%). In particular embodiments, provided herein are compositions comprising: a) a dermatologically acceptable carrier; and b) a functionalized fullerene compound, graphene, and / or carbon nanotubes, wherein said functionalized fullerene compound is present in said composition at a concentration of about 10% to about 20% (e.g., about 9% … 10%...11% … 12% … 13% … 14% … 15% … 16% … 17% … 18% … 19% … 20% or about 21%), wherein the composition has a gradual darkening shade of yellow color from very light yellow to very dark yellow depending on the concentration of said functionalized fullerene compound present, wherein a concentration of about 10% of said functionalized fullerene compound providing said very light yellow color to said composition, and wherein a concentration of about 20% of said functionalized fullerene compound providing said very dark yellow color. In certain embodiments, provided herein are kits and systems comprising: a) a container, and b) the composition described above or below, or otherwise herein. In some embodiments, the container comprises an opening that allows the composition to flow out therefrom in a controlled manner (e.g., sunscreen bottle or liquid foundation or primer type makeup). In other embodiments, the kits and systems further comprise a skin tone chart for Attorney Docket No.: CCF-41807.601 aiding a user in matching the composition (e.g., the composition in the container) to their own skin tone or skin tone of a person they are helping, and optionally wherein the skin tone chart is attached to the container (e.g., glued or integral with the container). In some embodiments, the container is Primary Cosmetic Packaging, which is optionally configured for dry or wet makeup. In particular embodiments, provided herein are methods of applying a generally skin- tone matching composition to the skin or hair of a subject comprising: applying the composition described above, below, or otherwise herein, to the skin or hair of a subject such that the composition generally matches the skin tone or surrounding skin tone, or hair color, of the subject. In some embodiments, the skin-tone matching composition generally matches the subject's skin tone or hair color, thereby minimizing the presence of the composition on the subject's skin or hair. In other embodiments, the subject is a human (e.g., human female or male, at the beach or in their bathroom). In certain embodiments, the composition provides sunscreen protection (e.g., prevents or reduces hyperpigmentation on skin, such as human skin). In other embodiments, the composition is applied for cosmetic effect. In some embodiments, provided herein are methods of making a skin care product comprising: mixing the composition described above, below, or otherwise herein with a sunscreen formulation or a cosmetic product (or haircare product) to achieve a desired shade of tan or brown tinting for the sunscreen formulation or the cosmetic product (or the haircare product). In certain embodiments, the sunscreen formulation or the cosmetic product (or the haircare product) has a white or light color prior to the mixing. In particular embodiments, the cosmetic product is makeup (e.g., foundation, primer, concealer, powder, etc.). In some embodiments, the dermatologically acceptable carrier is white or light in color prior to being in the composition and / or wherein the composition would have a generally white color if the functionalized fullerene compound were not present. In additional embodiments, the concentration of the functionalized fullerene compound is selected from: about 0.25%, about 0.5%, about 0.75%, about 1.0%, about 1.25%, about 1.5%, about 1.75%, about 2.0%, about 2.25%, about 2.5%, about 2.75%, and about 3.0%. In other embodiments, the composition further comprises titanium dioxide and / or zinc oxide (or other metal oxide). In particular embodiments, the composition comprises the titanium dioxide, and wherein the titanium dioxide is present in the composition at a concentration between 0.1% and 10% (e.g., 0.1% … 0.5 … 1.0% … 3.0% … 6.0% … 8.0% … 9.0% … or 10%). In certain embodiments, the titanium dioxide is present in the composition at a concentration of about 7.5%. In further embodiments, the composition comprises the zinc oxide, and wherein the zinc oxide is present in the composition at a Attorney Docket No.: CCF-41807.601 concentration between 0.1% and 10% (e.g., 0.1% … 0.5 … 1.0% … 3.0% … 6.0% … 8.0% … 9.0% … or 10%). In additional embodiments, the zinc oxide is present in the composition at a concentration of about 7.5%. In some embodiments, the composition comprises the zinc oxide and the titanium dioxide, and wherein the zinc oxide is present in the composition at a concentration between 0.1% and 10%, and wherein the titanium dioxide is present in the composition at a concentration between 0.1% and 10%. In further embodiments, the zinc oxide is present in the composition at a concentration of about 7.5%, and wherein the titanium dioxide is present in the composition at a concentration of about 7.5%. In additional embodiments, the compositions herein further comprise a sun protection factor (SPF) agent and / or a ultraviolet A protection factor (PFA) agent, that is not a fullerene composition. In other embodiments, the SPF or PFA agent is selected from the group consisting of: TiO2, ZnO, Avobenzone, Oxybenzone, Octocrylene, Octisalate, Homosalate, Octinoxate, Cinoxate, Dioxybenzone, Ensulizole, Meradimate, Padimate O, Sulisobenzone, PABA, Trolamine salicylate, Tinosorb S, Tinosorb A2B, Tinosorb M, Mexoryl SX, Ecamsule, Mexoryl XL, Uvinul A Plus, Neo Heliopan AP, Uvinul T 150, Amiloxate, Polysilicone-15, Iscotrizinol, Enzacamene, Triasorb, Camphor Benzalkonium Methosulfate, Benzophenone-3, or any combination thereof. In other embodiments, the SPF or PFA agent is: i) ZnO, ii) TiO2 and ZnO, iii) Avobenzone, or iv) ecamsule and / or ensulizole. In some embodiments, the fullerene compound is selected from: a hydroxy fullerene, a carboxy fullerene, a polyamino fullerene, pegylated fullerene, a fullerene hydride, and a halogenated fullerene. In other embodiments, the composition is free of a tan or brown colorant (or any other colorant) except for the functionalized fullerene compound. In other embodiments, the fullerene compound is a hydroxy fullerene according to the formula: C2n(OH)t(NH2)v(COOH)w(COOM)xOyMz, wherein: i) M is an alkali metal, alkaline earth metal, transition metal, post-transition metal, or lanthanide, ii) n is a number ranging from 10 to 270, iii) t is number ranging from 0 to 60, iv) v is a number ranging from 0 to 60, v) w is a number ranging from 0 to 60, vi) x is a numbering ranging from 0 to 60, vii) y is a number ranging from 0 to 30, viii) z is a number ranging from 0 to 30, and wherein (t+y)>z and t>y. In certain embodiments, wherein (t+y)>z and t>y; and / or wherein n is 25–42; and / or wherein t is 4-44; and / or wherein y is 1-44; and / or wherein z is 1-20. In further embodiments, the fullerene compound is selected from the group consisting of: C60(OH)9O7Na6; C60(OH)11O8Na5; C60(OH)11O12Na8; C60(OH)11O20Na10K6; C60(OH)6O4Na4; C60(OH)20O8Na4; C60(OH)10O13Na6; C60(OH)4O14Na17; C60(OH)13O4Na3; C60O13Na14; Gd@C82(OH)15O12Na5; Gd3N@C80(OH)13O9Na6; C60(OH)11O8S8Na5; C60(OH)11(SH)5O8Na5; C60C12N4H24; C60C12N6H30O12; and C60(OH)12O13Na13. Attorney Docket No.: CCF-41807.601 In further embodiments, the dermatologically acceptable carrier comprises a sunscreen lotion. In other embodiments, the dermatologically acceptable carrier comprises an emulsion selected from: a single emulsion, a double emulsion, or multiple emulsion. In further embodiments, the emulsion comprises a hydrophilic phase and a hydrophobic phase. In other embodiments, the hydrophobic phase comprises oil. In some embodiments, the oil is selected from the group consisting of: Red Raspberry Seed Oil, Carrot Seed Oil, Wheat Germ Oil, Almond Oil, Avocado Oil, Coconut Oil, Hemp Seed Oil, Jojoba Oil, Macadamia Oil, Olive Oil, Sesame Seed Oil, Shea Butter, a plant seed oil, and a synthetic oil, and any combination thereof. In certain embodiments, the dermatologically acceptable carrier comprises a cosmetic cream or lotion. In other embodiments, the dermatologically acceptable carrier comprises at least one of the following: Water, Cocoyl caprylate, Stearyl / octyldodecyl citrate crosspolymer, Polyhydroxystearic acid, Cetearyl olivate / sorbitan olivate, Benzyl alcohol- dehydroacetic acid, Cetearyl alcohol, Polyacrylate crosspolymer-6, xanthan gum, tetrasodium and EDTA. In particular embodiments, at least 25% or at least 50% of the composition comprises water by weight. In some embodiments, the fullerene compound selected from the following: C20, C24, C34, C36, C40, C44, C60, C72, C80, C82, C84, C96, C180, C240, C260, C320 and C540. In additional embodiments, the fullerene compound has a generally symmetrical spherical structure. In certain embodiments, the fullerene compound has a cage structure without internal atoms or is an endohedral fullerene. DESCRIPTION OF THE FIGURE Figures 1 shows a schematic representation of the chemical structure of a polyhydroxy fullerene (PHF) molecule (x=12 to 42). Figure 2 shows various sunscreen formulations that were made composed of various percent of titanium dioxide and / or zinc oxide, a carrier (composed of: Water, Cocoyl caprylate, Stearyl / octyldodecyl citrate crosspolymer, Polyhydroxystearic acid, Cetearyl olivate / sorbitan olivate, Benzyl alcohol-dehydroacetic acid, Cetearyl alcohol, Polyacrylate crosspolymer-6, xanthan gum, tetrasodium EDTA), and various percentages of "Photosorb" (e.g., in this example, PHF C60(OH)12O13Na13 was used) causing darker and darker tinting as percentages is increased between 0.25% and 2.5%. Figures 2A shows TiO2 = 0 wt%; ZnO = 0 wt%; PhotoSorb = 0 wt% (composition is generally white). Figure 2B shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 0 wt% (composition is generally white). Figure 2C shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 0.25 wt% (composition is generally Attorney Docket No.: CCF-41807.601 very light tan). Figure 2D shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 0.5 wt% (composition is light tan). Figure 2E shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 0.75 wt% (composition is generally tan). Figure 2F shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 1.25 wt% (composition is generally light brown). Figure 2G shows TiO2 = 7.5 wt%; ZnO = 7.5 wt%; PhotoSorb = 2.5 wt% (composition is generally brown). Figure 2H shows TiO2 = 0 wt%; ZnO = 0 wt%; PhotoSorb = 2.5 wt% (composition is generally dark brown). DEFINITIONS To facilitate an understanding of the present technology, a number of terms and phrases are defined below. Additional definitions are set forth throughout the detailed description. Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrase “in some embodiments” as used herein does not necessarily refer to the same embodiment, though it may. Furthermore, the phrase “in another embodiment” as used herein does not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments of the technology may be readily combined, without departing from the scope or spirit of the technology. In addition, as used herein, the term “or” is an inclusive “or” operator and is equivalent to the term “and / or” unless the context clearly dictates otherwise. In addition, throughout the specification, the meaning of “a”, “an”, and “the” include plural references. The meaning of “in” includes “in” and “on.” As used herein, the terms “subject” and “patient” refer to any animal, such as a mammal like a dog, cat, bird, livestock, and preferably a human. As used herein, “fullerene” refers a general class of molecules that exists essentially in the shape of a three dimensional polyhedron containing from 20 to 1500 carbon atoms, and which comprises carbon atoms as the predominant element from which they are composed. The fullerenes include but are not limited to C-28, C-32, C-44, C-50, C-58, C-60, C-70, C-84, C-94, C-250 and C-540. According to this nomenclature, the fullerene which contains 60 carbon atoms is denoted C-60, the fullerene which contains 70 carbon atoms is denoted C-70, etc. Also included among the fullerenes are the substituted fullerenes. These are molecular fullerenes which have had one or more of the atoms which comprise the fullerene cage structure replaced by an atom other than carbon, such as nitrogen, boron or titanium, yet essentially retain the geometry of a polyhedron upon being so substituted. Also included Attorney Docket No.: CCF-41807.601 among the fullerenes are endohedral fullerenes, in which atoms of elements other than carbon (e.g., iron, gadolinium and sulfur) reside inside the cage structure. Included in the term “fullerene” is a “functionalized fullerene” which refers to fullerene (Cx where x is 20 to 1500) with side groups attached to the outer surface of the cage via covalent bonds, ionic bonds, or Dewar coordination, or Kubas interactions, or any combination thereof. The side groups can be either inorganic, including, but not exclusive to, OH, Br, H2, Gd, Ti, organic, including, but not exclusive to, C(COOH)2, or any combination of organic and / or inorganic functional groups. The number of functional groups attached per cage of fullerene can vary from 1 to a majority of the number of carbons in the fullerene cage. Functionalized fullerenes have different physical and chemical properties based on the type and number of side groups. In certain embodiments, the fullerenes herein are compounds according to the formula to the formula: C2n(OH)t(NH2)v(COOH)w(COOM)xOyMz, wherein: M is an alkali metal, alkaline earth metal, transition metal, post-transition metal, or lanthanide, n is a number ranging from 10 to 270, t is number ranging from 0 to 60, v is a number ranging from 0 to 60, w is a number ranging from 0 to 60, x is a numbering ranging from 0 to 60, y is a number ranging from 0 to 30, and z is a number ranging from 0 to 30. In certain embodiments, (t+y)>z and t>y. Examples of fullerenes are found in U.S. Patent 9,950,977, U.S. Pat.10,925,817, and U.S. Pat. Pub.20210251860, all of which are herein incorporated by reference in their entireties, particularly for the fullerene compounds disclosed therein. In certain embodiments, the fullerenes employed herein are polyhydroxy fullerenes (PHFs). PHF has hydroxyl hemi-ketal, and carbonyl groups appended to fullerene cage, and is a salt of alkaline metals and / or alkaline earth metals. A “sunscreen composition” as used herein, is meant to include a composition for topical application to sun-exposed areas of the skin and / or hair of mammals, especially humans. Such a composition may be generally classified as leave-on or rinse off, and includes any product applied to a human body including an active agent that protects the skin against UV-induced damage, and includes products that also improving appearance, cleansing, odor control or provide improved general aesthetics. The term “dermatologically acceptable,” as used herein, means that the compositions or components described are suitable for use in contact with human skin, generally without significant risk of toxicity, incompatibility, instability, allergic response, and the like. Attorney Docket No.: CCF-41807.601 DETAILED DESCRIPTION Provided herein are compositions, systems, kits, and methods for using various low concentrations of functionalized fullerenes (e.g., polyhydroxy fullerenes), functionalzied graphene (e.g., graphene oxide), and / or functionalized carbon nanotubes (e.g., carboxylated multiwalled carbon nanotubes), to generate tinted skin care compositions, such as sunscreens and cosmetics, that a user can apply to generally match their skin tone. In certain embodiments, the compositions, kits, and systems herein comprise a dermatologically acceptable carrier (e.g., that is white or light in color prior to being in the composition) and a functionalized fullerene compound, functionalized graphene, and / or functionalized carbon nanotubes, for tinting present at a concentration of about 0.1% (e.g., for very light tan) to about 3.0% (e.g., for very dark brown). In certain embodiments, the compositions herein are present in a container, such as a sunscreen container or makeup container. Sunscreens and skin care products are currently and generally white in color. There is a need for tinted skin care products to reduce hyperpigmentation as well as match with different skin tones. Tinting is usually achieved with synthetic dyes or minerals. Several synthetics dyes have been found to be harmful by FDA and has been banned for this purpose. Minerals such as iron oxide are currently used in some tinted skin care products. Iron oxide serves a single purpose of imparting color and is not safe for the environment. Provided herein are composition that use polyhydroxy fullerenes, and other fullerenes, as a colorant for imparting natural skin colors to skin care products and sunscreens. Polyhydroxy fullerenes are safe to humans and the environment. In some embodiments, the fullerenes comprise polyhydroxy fullerenes. In other embodiments, the fullerenes are compounds according to the formula C2n(OH)t(SH)u(NH2)v(COOH)w(COOM)xOyMz, wherein M is an alkali metal, alkaline earth metal, transition metal, post-transition metal, lanthanide or actinide, n is a number ranging from 10 to 270; and t, u, v, w, x, y and z can range from 0 to the total number of carbon atoms present in the cage. Exemplary polyhydroxy fullerenes are disclosed in US8,883,124, US9,475,028, US9,950,977, US9,084.989, and US9,731,013 (all five of which are herein incorporated by reference in their entireties, particularly for polyhydroxy fullerene formulas). In certain embodiments, the fullerene has the following formula C60(OH)12O13Na13 or C60(OH)11O20Na10K6. Attorney Docket No.: CCF-41807.601 EXAMPLES EXAMPLE 1 Skin Irritation Study This Example describes skin irritation study conducted for polyhydroxy fullerenes (PHF) following OECD test guideline (TG 439) with the EpiDerm (EPI-200) reconstructed human skin tissue model. The PHF employed is a mixture provided by Suzhou Dade Technologies, which includes PHFs with an empirical formula of C60(OH)xOyNaz. The potential structures in this mixture are believed to include the following four species: i) C60(OH)17O16Na23; ii) C60(OH)10O12Na13; iii) C60(OH)13O9Na6; and / or C60(OH)12O12Na10. The EpiDerm skin tissues were placed into each well of a 6-well plate with 0.9 mL of media and were equilibrated for 60 minutes at standard culture conditions (SCC). The tissues were then transferred into new wells in a 6-well plate with media and incubated for 16 hours and 50 minutes at SCC. After incubation, the tissues were treated with negative control (Dulbecco’s phosphate buffered saline; DPBS), positive control (5% sodium dodecyl sulfate; SDS), and a PHF formulation in different concentrations for three replicates. A PHF gel was prepared by dissolving the polyhydroxy fullerenes in carrier vehicle containing 5 wt% glycerol and 5 wt% hydroxypropyl methylcellulose. Tissues were incubated at SCC for 35 minutes with various treatments, then placed in a biological safety cabinet for the remaining 60-min exposure. To rinse the tissue, the tissue inserts were filled and emptied with sterile DPBS 15 times, then completely submerged 3 times in 150 mL DPBS. The tissues were also rinsed from inside and outside with sterile DPBS. Any remaining DPBS was removed by gentle shaking and blotting the inserts before being transferred to 6-well plates pre-filled with 0.9 mL fresh assay for 26 hours. Media was replaced after 26 hours for 20 more hours of incubation at SCC. The tissues were then placed into the MTT reagent pre-warmed wells and incubated for an additional 3 hours. Tissues were removed from the reagent, blotted dry, and put into a new 24-well plate.2 mL of extractant solution was placed with each tissue and shaken for 2 hours. Tissue was removed and the optical density of the extracted solutions were measured with a spectrophotometer at 570 nm using 200 μL extractant as a blank. The percent viability of the tissue was calculated as the average optical density of the extractant from tissue of interest divided by the average optical density of the extractant from control tissue. The mean tissue viability being ≤ 50% is labeled as an irritant, while the mean tissue viability being > 50% is non-irritant. The mean percent tissue viability of the negative control (DPBS), positive control (SDS), and PHF formulations are shown in Table-1. The negative control had a mean tissue viability of 100%, while the positive control was 3.7% as Attorney Docket No.: CCF-41807.601 expected. All PHF concentrations tested exhibited a mean tissue viability of > 50% and therefore, the PHFs are not a skin irritant. TABLE 1 - Skin Irritation Mean SD of Mean SD Sample Prediction OD OD Viability Negative Control 1.11 NI Positive Control Polyhydroxy Polyhydroxy 3.33 NI Polyhydroxy Polyhydroxy Polyhydroxy Polyhydroxy Eye Irritation Study This Example describes eye irritation study conducted for polyhydroxy fullerenes formulations (PHFs) following OECD test guideline (TG 492) with the EpiOcular (OCL-200) tissue from MatTek. The PHF employed is a mixture provided by Suzhou Dade Technologies, which includes PHFs with an empirical formula of C60(OH)xOyNaz. The potential structures in this mixture are believed to include the following four species: i) C60(OH)17O16Na23; ii) C60(OH)10O12Na13; iii) C60(OH)13O9Na6; and / or C60(OH)12O12Na10. The EpiOcular tissues were placed into each well of a 6-well plate with 1 mL of media and were equilibrated for 60 minutes at standard culture conditions (SCC). The tissues were then transferred into new wells in a 6-well plate with media and incubated overnight at SCC. After overnight incubation, the tissues were treated with negative control (water), positive control (methyl acetate), and PHFs different concentrations for three replicates. PHF gel embodiments were prepared by dissolving polyhydroxy fullerenes in carrier vehicle containing 5 wt% glycerol and 5 wt% hydroxypropyl methylcellulose. Tissues were incubated at SCC for 30 minutes with various treatments. At the end of incubation, the treatment was removed by rinsing the tissues with approximately 100 mL of DPBS for three Attorney Docket No.: CCF-41807.601 times. The tissues were then soaked in SCC medium for 12 minutes to remove any remaining treatment. Subsequently, the tissues were taken out and blotted to remove excess medium and placed in a 6-well plate with media and incubated for 120 minutes at SCC. The tissues were then placed into the MTT reagent pre-warmed wells and incubated for an additional 3 hours. Tissues were removed from the reagent, blotted dry, and put into a new 24-well plate.2 mL of extractant solution was placed with each tissue and shaken for 2 hours. Tissue was removed and the optical density of the extracted solutions were measured with a spectrophotometer at 570 nm using 200 μL extractant as a blank. TABLE 2 - Eye Irritation Mean SD Sample Prediction Viabilit Viabilit The percent viability of the tissue was calculated as the average optical density of the extractant from tissue of interest divided by the average optical density of the extractant from control tissue. The mean tissue viability being ≤ 60% is labeled as an irritant, while the mean tissue viability being > 60% is non-irritant. The mean percent tissue viability of the negative control (water), positive control (methyl acetate), and PHF formulations are shown in Table 2. The negative control had a mean tissue viability of 100%, while the positive control was 47.6% as expected. All PHF concentrations tested exhibited a mean tissue viability of > 60% and therefore, these PHFs are not an eye irritant. Attorney Docket No.: CCF-41807.601 REFERENCES: 1. U.S. Pat.10,925,817 2. Bikiaris et al., Appl. Nano 2022, 3, 1–15. All publications and patents mentioned in the specification and / or listed below are herein incorporated by reference. Various modifications and variations of the described method and system of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention that are obvious to those skilled in the relevant fields are intended to be within the scope described herein.

Claims

Attorney Docket No.: CCF-41807.601 CLAIMS We Claim:

1. A composition comprising: a) a dermatologically acceptable carrier; and b) at least one compound selected from: a functionalized fullerene compound, functionalized graphene, and functionalized carbon nanotubes, wherein said functionalized fullerene compound, if present, is present in said composition at a concentration of about 0.1% to 3.0%, wherein said functionalized graphene, if present, is present in said composition at a concentration of about 0.01% to 1.0% by weight, wherein said functionalized carbon nanotubes, if present, are present in said composition at a concentration of about 0.01% to 1.0% by weight, and optionally: wherein said composition has a gradual darkening shade of brown color from very light tan to very dark brown depending on: i) the concentration of said functionalized fullerene compound present, ii) concentration of said functionalized graphene present, or iii) concentration of said functionalized carbon nanotubes present, wherein a concentration of: i) about 0.1% of said functionalized fullerene compound, ii) about 0.01% by weight of said functionalized graphene, or iii) about 0.01% of said functionalized carbon nanotubes provides said very light tan color to said composition, and wherein a concentration of: i) about 3.0% of said functionalized fullerene compound, ii) about 1.0% by weight of said functionalized graphene, or iii) about 1.0% by weight of said functionalized carbon nanotubes provides said very dark brown color.

2. The composition of claim 1, wherein said dermatologically acceptable carrier is white or light in color prior to being in said composition and / or wherein said composition would have a generally white color if said at least one compound were not present.

3. The composition of claim 1, wherein said concentration of said functionalized fullerene compound is selected from: about 0.25%, about 0.5%, about 0.75%, about 1.0%, about 1.25%, about 1.5%, about 1.75%, about 2.0%, about 2.25%, about 2.5%, about 2.75%, and about 3.0%; and / or wherein said concentration of said functionalized graphene or functionalized carbon nanotubes is selected from: about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 0.75%, or about 1.0%.Attorney Docket No.: CCF-41807.601 4. The composition of claim 1, wherein said composition further comprises titanium dioxide and / or zinc oxide.

5. The composition of claim 4, wherein said composition comprises said titanium dioxide, and wherein said titanium dioxide is present in said composition at a concentration between 0.1% and 20% or between 0.1% and 10%.

6. The composition of claim 5, wherein said titanium dioxide is present in said composition at a concentration of about 7.5%.

7. The composition of claim 4, wherein said composition comprises said zinc oxide, and wherein said zinc oxide is present in said composition at a concentration between 0.1% and 20% or between 0.1% and 10%.

8. The composition of claim 7, wherein said zinc oxide is present in said composition at a concentration of about 7.5%.

9. The composition of claim 4, wherein said composition comprises said zinc oxide and said titanium dioxide, and wherein said zinc oxide is present in said composition at a concentration between 0.1% and 20% or between 0.1% and 10%, and wherein said titanium dioxide is present in said composition at a concentration between 0.1% and 20%, or between 0.1% and 10%.

10. The composition of claim 9, wherein said zinc oxide is present in said composition at a concentration of about 7.5%, and wherein said titanium dioxide is present in said composition at a concentration of about 7.5%.

11. The composition of claim 1, further comprising a sun protection factor (SPF) agent and / or a ultraviolet A protection factor (PFA) agent.

12. The composition of claim 11, wherein said SPF or PFA agent is selected from the group consisting of: TiO2, ZnO, Avobenzone, Oxybenzone, Octocrylene, Octisalate, Homosalate, Octinoxate, Cinoxate, Dioxybenzone, Ensulizole, Meradimate, Padimate O,Attorney Docket No.: CCF-41807.601 Sulisobenzone, PABA, Trolamine salicylate, Tinosorb S, Tinosorb A2B, Tinosorb M, Mexoryl SX, Ecamsule, Mexoryl XL, Uvinul A Plus, Neo Heliopan AP, Uvinul T 150, Amiloxate, Polysilicone-15, Iscotrizinol, Enzacamene, Triasorb, Camphor Benzalkonium Methosulfate, Benzophenone-3, or any combination thereof.

13. The composition of claim 11, wherein said SPF or PFA agent is: i) ZnO, ii) TiO2 and ZnO, iii) Avobenzone, or iv) ecamsule and / or ensulizole.

14. The composition of claim 1, wherein said fullerene compound is selected from: a hydroxy fullerene, a carboxy fullerene, a polyamino fullerene, pegylated fullerene, a fullerene hydride, and a halogenated fullerene, and / or said graphene comprises graphene oxide, reduced graphene oxide, and aminate graphene and / or wherein said caron nanotubes comprise hydroxylated nanotubes, aminated nanotubes, and carboxylated multiwalled carbon nanotubes.

15. The composition of claim 1, wherein said composition is free of a brown or tan colorant except for said at least one compound.

16. The composition of claim 1, wherein said fullerene compound is present and is a hydroxy fullerene according to the formula: C2n(OH)t(NH2)v(COOH)w(COOM)xOyMz, wherein: i) M is an alkali metal, alkaline earth metal, transition metal, post- transition metal, or lanthanide, ii) n is a number ranging from 10 to 270, iii) t is number ranging from 0 to 60, iv) v is a number ranging from 0 to 60, v) w is a number ranging from 0 to 60, vi) x is a numbering ranging from 0 to 60, vii) y is a number ranging from 0 to 30, viii) z is a number ranging from 0 to 30, and wherein (t+y)>z and t>y.

17. The composition of claim 16, wherein (t+y)>z and t>y; and / or wherein n is 25–42; and / or wherein t is 4-44; and / or wherein y is 1-44; and / or wherein z is 1-20.Attorney Docket No.: CCF-41807.601 18. The composition of claim 1, wherein said fullerene compound is present and is selected from the group consisting of: i) C60(OH)17O16Na23; ii) C60(OH)10O12Na13; iii) C60(OH)13O9Na6; and / or C60(OH)12O12Na10, and iv) mixtures of 2 or more thereof.

19. The composition of claim 1, wherein said dermatologically acceptable carrier comprises a sunscreen lotion, cream, or makeup.

20. The composition of claim 1, wherein said dermatologically acceptable carrier comprises an emulsion selected from: a single emulsion, a double emulsion, or multiple emulsion.

21. The composition of claim 20, wherein said emulsion comprises a hydrophilic phase and a hydrophobic phase.

22. The composition of claim 21, wherein said hydrophobic phase comprises oil.

23. The composition of Claim 22, wherein said oil is selected from the group consisting of: Red Raspberry Seed Oil, Carrot Seed Oil, Wheat Germ Oil, Almond Oil, Avocado Oil, Coconut Oil, Hemp Seed Oil, Jojoba Oil, Macadamia Oil, Olive Oil, Sesame Seed Oil, Shea Butter, a plant seed oil, and a synthetic oil, and any combination thereof.

24. The composition of claim 1, wherein said dermatologically acceptable carrier comprises a cosmetic cream or lotion.

25. The composition of claim 1, wherein said dermatologically acceptable carrier comprises at least one of the following: Water, Cocoyl caprylate, Stearyl / octyldodecyl citrate crosspolymer, Polyhydroxystearic acid, Cetearyl olivate / sorbitan olivate, Benzyl alcohol- dehydroacetic acid, Cetearyl alcohol, Polyacrylate crosspolymer-6, xanthan gum, tetrasodium and EDTA.

26. The composition of claim 1, wherein at least 25% or at least 50% of said composition comprises water by weight.Attorney Docket No.: CCF-41807.601 27. The composition of claim 1, wherein said fullerene compound is present and is selected from the following: C20, C24, C34, C36, C40, C44, C60, C72, C80, C82, C84, C96, C180, C240, C260, C320 and C540.

28. The composition of claim 1, wherein said fullerene compound is present and has a generally symmetrical spherical structure.

29. The composition of claim 1, wherein said fullerene compound is present and has a cage structure without internal atoms or is an endohedral fullerene.

30. A kit or system comprising: a) a container, and b) said composition of any of claims 1-29 or 43.

31. The kit or system of claim 30, wherein said container comprises an opening that allows said composition to flow out therefrom in a controlled manner.

32. The kit or system of claim 30, further comprising a skin tone chart for aiding a user in matching said composition to their own skin tone, and optionally wherein said skin tone chart is attached to said container.

33. The kit or system of claim 30, wherein said container is a bottle, which is optionally configured for sunscreen.

34. The kit or system of claim 30, wherein said container is Primary Cosmetic Packaging, which is optionally configured for dry or wet makeup.

35. A method of applying a generally skin-tone matching composition to the skin or hair of a subject comprising: applying said composition of any of claims 1-29 or 43 to the skin or hair of a subject such that said composition generally matches the skin tone or surrounding skin tone, or hair color, of the subject.

36. The method of claim 35, wherein the skin-tone matching composition generally matches the subject's skin tone or hair color, thereby minimizing the presence of the composition on the subject's skin or hair.Attorney Docket No.: CCF-41807.601 37. The method of claim 35, wherein said subject is a human.

38. The method of claim 35, wherein said composition provides sunscreen protection.

39. The method of claim 35, wherein said composition is applied for cosmetic effect.

40. A method of making a skin care product comprising: mixing the composition of any of claims 1-29 with a sunscreen formulation or a cosmetic product to achieve a desired shade of brown tinting for said sunscreen formulation or said cosmetic product.

41. The method of claim 40, wherein said sunscreen formulation or said cosmetic product has a white or light color prior to said mixing.

42. The method of claim 40, wherein said cosmetic product is makeup.

43. A composition comprising: a) a dermatologically acceptable carrier; and b) a functionalized fullerene compound, and / or graphene, and / or carbon nanotubes, wherein said functionalized fullerene compound, if present, is present in said composition at a concentration of about 10% to about 20%, wherein said composition has a gradual darkening shade of yellow color from very light yellow to very dark yellow depending on the concentration of said functionalized fullerene compound present, wherein a concentration of about 10% of said functionalized fullerene compound providing said very light yellow color to said composition, and wherein a concentration of about 20% of said functionalized fullerene compound providing said very dark yellow color.

Images