Novel metal-organic framework having antioxidant activity and antioxidant cosmetic composition comprising same

Abstract

The present invention relates to a novel metal-organic framework capable of maintaining and / or enhancing antioxidant activity even upon prolonged exposure to light, and a cosmetic composition comprising same, wherein the novel metal-organic framework of the present invention can exhibit excellent antioxidant activity, maintain antioxidant activity for an extended period of time, and, even upon prolonged exposure to light, does not exhibit a decrease in antioxidant activity and can maintain and / or enhance the antioxidant activity. In addition, the antioxidant cosmetic composition comprising the aforementioned novel metal-organic framework does not exhibit a decrease in antioxidant activity due to light, even when applied to skin areas exposed to the external environment, such as the face or arms.

Description

Novel metal-organic framework having antioxidant activity and antioxidant cosmetic composition containing the same

[0001] The present invention relates to a novel metal-organic framework having antioxidant activity and an antioxidant cosmetic composition containing the same.

[0002] Human skin is the organ that occupies the largest surface area of ​​the body and is constantly exposed to the external environment. Skin performs a role beyond that of a simple protective barrier. It protects the body from physical friction, prevents water loss, and shields it from harmful ultraviolet rays. Furthermore, it plays an essential role in maintaining health by regulating body temperature and actively generating and eliminating new cells.

[0003] However, as the skin is in constant contact with the external environment, it is vulnerable to oxidative stress caused by free radicals. Free radicals accelerate skin aging and can be a cause of various diseases, such as cancer. Accordingly, research on antioxidants that inhibit the oxidative reactions of free radicals has been actively conducted.

[0004] Widely known antioxidants to date include polyphenol compounds, flavonoids, tocopherols, and vitamin C. While these substances possess antioxidant efficacy in themselves, they reveal several limitations when applied directly to the skin. For example, natural antioxidants often fail to produce sufficient effects, and synthetic antioxidants face restrictions on use due to safety concerns despite their excellent efficacy.

[0005] In particular, Vitamin C, widely used in cosmetics and known as the most powerful antioxidant, has a fatal flaw. Its antioxidant function deteriorates rapidly upon exposure to light, making it difficult to expect any effect when applied to the skin. This is the main reason why cosmetics containing Vitamin C fail to properly exert their antioxidant effects.

[0006] There is a growing demand for new materials that can overcome the limitations of existing antioxidants and maintain stable antioxidant efficacy even under external stimuli such as light.

[0007] [Prior Art Literature]

[0008] [Patent Literature]

[0009] KR 10-2022-0068350 A1

[0010] The object of the present invention is to provide a novel metal-organic framework having antioxidant activity and an antioxidant cosmetic composition containing the same.

[0011] Another objective of the present invention is to provide a novel metal-organic framework capable of exhibiting excellent antioxidant capacity, maintaining antioxidant capacity for a long time, and maintaining and / or enhancing antioxidant capacity without degradation even when exposed to light for a long time.

[0012] Another objective of the present invention is to provide an antioxidant cosmetic composition comprising the novel metal-organic framework described above, wherein the antioxidant capacity is not reduced by light even when applied to skin exposed to the outside, such as the face or arms.

[0013] To achieve the above-mentioned objective, the present invention may relate to a novel metal-organic framework comprising a metal ion or metal cluster; and at least one organic ligand that forms a bond with the metal ion to form a metal-organic framework (MOF), wherein the organic ligand exhibits an antioxidant effect.

[0014] In addition, the metal-organic framework may additionally have a ligand compound represented by the following chemical formula 1 bonded to it:

[0015] [Chemical Formula 1]

[0016]

[0017] Here,

[0018] n is an integer of 1 or 2, and

[0019] EDP ​​refers to a group containing an electron pair donor atom, and

[0020] L1 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, and a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms.

[0021] In addition, the ligand compound represented by Chemical Formula 1 above may be a ligand compound represented by Chemical Formula 2 or Chemical Formula 3 below:

[0022] [Chemical Formula 2]

[0023]

[0024] [Chemical Formula 3]

[0025]

[0026] Here,

[0027] EDP ​​is as defined in Chemical Formula 1 above, and

[0028] m is an integer from 1 to 4, and

[0029] p is an integer of 0 or 1, and

[0030] L2 is selected from the group consisting of a single bond, a carbonyl group, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms.

[0031] X1 and X2 are identical or different from each other, and each is independently N or C(R3), and

[0032] R1 to R3 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 of It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0033] In addition, the metal cluster may include a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi.

[0034] In addition, the metal ion is Li + , Na + , Mg 2+ , Ca 2+ , Sr 2+ , Ba2+ , Sc 3+ , Y 3+ , You 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Yes 3+ , Cr 3+ , My 3+ , W 3+ , Mr. 3+ , Mr. 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , If 3+ , If 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ireland 3+ , Ireland 2+ , Ireland + , We 2+ , We + , Pd 2+ , Pd + , Pt 2+ , Pt + , Dog 2+ , Dog + , At + , Oh + , Zn 2+ , CD 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Yes 4+ , Yes 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + It can be selected from a group consisting of

[0035] In addition, the metal-organic framework may be selected from the group consisting of aluminum-based metal-organic frameworks, iron-based metal-organic frameworks, zirconium-based metal-organic frameworks, magnesium-based metal-organic frameworks, zinc-based metal-organic frameworks, and mixtures thereof.

[0036] In addition, the organic ligand is 1,3,5-benzenetricarboxylic acid, 4,4'-biphenyldicarboxilic acid, benzene-1,4-dicarboxylic acid, 9,10-anthracenedicarboxylic acid, biphenyl-3,3,5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 5-bromoisophthalic acid, 5-cyano-1,3-benzenedicarboxylic acid, 2,2-diamino4,4'-stilbenedicarboxylic acid, 2,5-diaminoterephthalic acid, 1,1,2,2-tetra(4-carboxylphenyl)ethylene, 2,5-dihydroxyterephthalic acid, 2,2-dinitro-4,4-stilbenedicarboxylic acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 2-hydroxyterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 4,4,4''-s-triazine-2,4,6-triyl-tribenzoic acid4,6-triyltribenzoic acid), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-triscarboxyphenylethynylbenzene, 2-methylimidazole and It may be one or more selected from the group consisting of 2-aminoterephthalic acid.

[0037] In addition, the above metal-organic framework can exhibit a sustained antioxidant effect as the organic ligand degrades over time.

[0038] In addition, the above metal-organic framework can maintain its antioxidant capacity even after more than 200 hours.

[0039] In addition, the above metal-organic framework may increase its antioxidant capacity by 0.1% to 30% when exposed to light for 24 hours.

[0040] To achieve the above-mentioned purpose, the present invention may be a cosmetic composition having antioxidant activity comprising the novel metal-organic framework described above.

[0041] In the present invention, “hydrogen” is hydrogen, light hydrogen, deuterium, or tritium.

[0042] In the present invention, the “halogen group” is fluorine, chlorine, bromine, or iodine.

[0043] In the present invention, “alkyl” refers to a monovalent substituent derived from a straight-chain or side-chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0044] In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0045] In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0046] In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, consisting of a single ring or a combination of two or more rings. Additionally, forms in which two or more rings are simply pendent or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, etc.

[0047] In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Additionally, forms in which two or more rings are simply pendent or condensed with each other may be included, and furthermore, forms condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0048] In the present invention, "aralkyl" refers to an aryl-alkyl group such as aryl and alkyl as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl, and naphthalenylmethyl. Bonding to the parent residue is made through alkyl groups.

[0049] In the present invention, “heteroarylalkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

[0050] In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

[0051] In the present invention, "forming a ring by combining with adjacent groups" means combining with adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heteroring; a substituted or unsubstituted aromatic heteroring; or a condensed ring thereof.

[0052] In the present invention, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution location is not limited to the location where the hydrogen atom is substituted, that is, any location where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0053] The present invention is a novel metal-organic framework that can exhibit excellent antioxidant capacity, maintain antioxidant capacity for a long time, and maintain and / or improve antioxidant capacity without decreasing even when exposed to light for a long time.

[0054] In addition, the antioxidant cosmetic composition containing the novel metal-organic framework described above does not lose its antioxidant capacity due to light even when applied to externally exposed skin, such as the face or arms.

[0055] FIG. 1 is a schematic diagram of a metal-organic framework according to one embodiment of the present invention.

[0056] Figure 2 is a scanning electron microscope observation result of a metal-organic framework according to one embodiment of the present invention.

[0057] Figure 3 is the result of X-ray diffraction analysis of a metal-organic framework according to one embodiment of the present invention.

[0058] Figure 4 is the result of BET analysis through N2 adsorption of a metal-organic framework according to one embodiment of the present invention.

[0059] Figure 5 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for UIO-66 according to one embodiment of the present invention.

[0060] Figure 6 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for UIO-67 according to one embodiment of the present invention.

[0061] Figure 7 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for UIO66-NH2 according to one embodiment of the present invention.

[0062] Figure 8 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for AL101NH2 according to one embodiment of the present invention.

[0063] Figure 9 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for MIL88-NH2 according to one embodiment of the present invention.

[0064] Figure 10 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for MgMOF74 according to one embodiment of the present invention.

[0065] Figure 11 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for ZIF8 according to one embodiment of the present invention.

[0066] FIG. 12 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for FE101NH2 according to one embodiment of the present invention.

[0067] FIG. 13 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for MOF-525 according to one embodiment of the present invention.

[0068] FIG. 14 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for MOF-808 according to one embodiment of the present invention.

[0069] FIG. 15 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-ABA according to one embodiment of the present invention.

[0070] FIG. 16 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-ALA according to one embodiment of the present invention.

[0071] FIG. 17 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-AIA according to one embodiment of the present invention.

[0072] FIG. 18 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-PTA according to one embodiment of the present invention.

[0073] FIG. 19 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-ABZ according to one embodiment of the present invention.

[0074] FIG. 20 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-GAB according to one embodiment of the present invention.

[0075] FIG. 21 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-LS according to one embodiment of the present invention.

[0076] FIG. 22 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-MNA according to one embodiment of the present invention.

[0077] FIG. 23 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-APD according to one embodiment of the present invention.

[0078] FIG. 24 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-DAT according to one embodiment of the present invention.

[0079] FIG. 25 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-MB according to one embodiment of the present invention.

[0080] FIG. 26 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO67-MN according to one embodiment of the present invention.

[0081] FIG. 27 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO66-AIA according to one embodiment of the present invention.

[0082] FIG. 28 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for UIO66-ABZ according to one embodiment of the present invention.

[0083] FIG. 29 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for MIL101NH2-ABZ according to one embodiment of the present invention.

[0084] FIG. 30 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for MIL101NH2-AIA according to one embodiment of the present invention.

[0085] Figure 31 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption, and cytotoxicity evaluation results for MgMOF74-ABZ according to one embodiment of the present invention.

[0086] FIG. 32 shows the scanning electron microscope observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption and cytotoxicity evaluation results for MgMOF74-AIA according to one embodiment of the present invention.

[0087] Figure 33 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0088] Figure 34 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0089] Figure 35 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0090] Figure 36 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0091] Figure 37 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0092] Figure 38 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0093] FIG. 39 is the experimental result of the antioxidant effect of a metal-organic framework through an ORAC assay according to one embodiment of the present invention.

[0094] FIG. 40 is the experimental result of the antioxidant effect of an organic ligand through an ORAC assay according to one embodiment of the present invention.

[0095] Figure 41 is the experimental result of the antioxidant effect of an organic ligand according to one embodiment of the present invention through an ORAC assay.

[0096] Figure 42 is an experimental result confirming whether an organic ligand of a metal-organic framework is released according to one embodiment of the present invention.

[0097] Figure 43 is an experimental result regarding the variation in antioxidant effect of a metal-organic framework irradiated with ultraviolet rays according to one embodiment of the present invention.

[0098] Figure 44 is an experimental result regarding the variation in antioxidant effect of a metal-organic framework irradiated with ultraviolet light according to one embodiment of the present invention.

[0099] FIG. 45 is an experimental result regarding the variation in antioxidant effect of a metal-organic framework according to one embodiment of the present invention upon UV irradiation.

[0100] Figure 46 is an experimental result regarding the variation in antioxidant effect of a metal-organic framework irradiated with ultraviolet rays according to one embodiment of the present invention.

[0101] FIG. 47 is an experimental result regarding the variation in antioxidant effect of a metal-organic framework irradiated with ultraviolet light according to one embodiment of the present invention.

[0102] The present invention relates to a novel metal-organic framework comprising a metal ion or metal cluster; and at least one organic ligand that forms a bond with the metal ion to form a metal-organic framework (MOF), and which exhibits an antioxidant effect through the organic ligand.

[0103] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0104] Vitamin C, also known as ascorbic acid, is the most powerful and broad-spectrum antioxidant among intracellular antioxidant vitamins. It plays a role in eliminating free radicals by preventing oxygen from reacting with them, and it also repairs DNA damaged by free radicals.

[0105] In general, vitamin C is considered to play an important antioxidant role in the lens and plasma. Additionally, vitamin C is a representative water-soluble antioxidant, and its mechanism of action can be summarized in two ways.

[0106] First, it reacts with and inactivates reactive oxygen species in the body's aqueous parts, such as cytoplasm, plasma, and extracellular fluid, and performs independent functions in aqueous solutions, primarily +3 valent iron (Fe3 +{ ) +2 iron (Fe 2+ It reduces the activity of lipoxygenase, an enzyme that peroxidizes lipids, by reducing it to ).

[0107] Second, it has the function of regenerating the oxidized form of Vitamin E, which very effectively prevents lipid oxidation. However, hydrophilic antioxidant nutrients such as Vitamin C effectively remove water-soluble reactive oxygen species but cannot remove them within the cell membrane, so they have the disadvantage of not being able to function as antioxidant nutrients that inhibit chain reactions.

[0108] In addition, regarding skin aging, Vitamin C is known to play an important role in whitening by synthesizing collagen, a connective tissue in the dermis, maintaining elasticity, and preventing the deposition of melanin pigment in the skin.

[0109] In addition, Vitamin C is used as an ingredient in many cosmetics because it has the function of protecting the skin from external environmental factors that can cause damage and from photoaging.

[0110] However, because Vitamin C is water-soluble, it is generally present in small quantities in products, or its unstable state within cosmetics may prevent it from being efficiently delivered to the skin. In particular, natural Vitamin C is easily decomposed by oxygen and light, and being acidic, it can irritate the skin.

[0111] Currently, various cosmetics containing Vitamin C are being sold on the market, and due to the aforementioned problem, various methods of use are being suggested to maintain or enhance the antioxidant effect through cosmetics containing Vitamin C.

[0112] For example, it is best to apply Vitamin C cosmetics first after cleansing with a mildly acidic cleanser. Since they require sufficient time and action to facilitate absorption without causing environmental changes to a pH of 4 or lower, it is recommended to apply them slowly and repeatedly in small amounts to ensure proper absorption. Therefore, while cosmetics are generally applied in the order of toner, essence, lotion, and cream, it is recommended to apply Vitamin C cosmetics before toner.

[0113] As mentioned above, despite the inconvenience of the usage methods, cosmetics containing Vitamin C are used because Vitamin C exhibits excellent antioxidant effects. However, Vitamin C, which exhibits such excellent antioxidant effects, has the problem of being easily decomposed by oxygen and light, making it unable to maintain its antioxidant capacity.

[0114] Accordingly, the present invention relates to a novel material that is not degraded by light and can maintain and / or enhance its antioxidant capacity. That is, when applied to the skin, the antioxidant capacity of the novel material is not reduced even when exposed to sunlight for a long time, and is characterized by maintaining the initial antioxidant capacity or, on the contrary, exhibiting an effect of increasing the antioxidant capacity.

[0115] The novel material of the present invention comprises a metal ion or metal cluster; and at least one organic ligand that forms a bond with the metal ion to form a metal-organic framework (MOF), and can exhibit an antioxidant effect through the organic ligand.

[0116] The above metal-organic framework is formed by coordination bonding between a metal or metal cluster and an organic material or linker. Specifically, a "metal-organic framework (MOF)" refers to a porous material in which metal clusters and organic linkers (or organic bridging ligands) are connected by coordination bonds to form a three-dimensional structure; various MOFs can be created depending on the selection of metal ions and organic ligands. The aforementioned MOF is characterized by its porosity, which contains empty spaces within its structure, and the pore size, porosity, three-dimensional structure, and surface area can be designed in various ways depending on the types and bonding methods of the metal ions and organic ligands constituting the MOF. Due to this porosity, MOFs not only possess a very large surface area but also an open pore structure; consequently, compared to other known porous materials, they enable the movement of large quantities of molecules or solvents. Furthermore, when used as catalysts or gas storage materials, they offer the advantage of maximizing efficiency due to the abundance of active sites. Additionally, the MOF does not easily deform at high temperatures and possesses a rigid framework, which contributes to chemical stability and thermal resistance. It has excellent stability.

[0117] As can be confirmed in the experimental examples described below, the organic ligand included in the metal-organic framework of the present invention can exhibit an antioxidant effect. Accordingly, the metal-organic framework can exhibit an antioxidant effect through the organic ligand, and as the metal-organic framework decomposes and releases the organic ligand over time, it can exhibit a continuous antioxidant effect for a long period.

[0118] Due to these effects, the metal-organic framework of the present invention does not have its antioxidant effect reduced by strong light such as ultraviolet rays, and even if the metal-organic framework is degraded by light, the organic ligand acts within the skin to further enhance the antioxidant effect.

[0119] In addition, the organic linker or organic ligand is 1,3,5-benzenetricarboxylic acid, 4,4'-biphenyldicarboxilic acid, benzene-1,4-dicarboxylic acid, 9,10-anthracenedicarboxylic acid, biphenyl-3,3,5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 5-bromoisophthalic acid, 5-cyano-1,3-benzenedicarboxylic acid, 2,2-diamino4,4'-stilbenedicarboxylic acid, 2,5-diaminoterephthalic acid, 1,1,2,2-tetra(4-carboxylphenyl)ethylene, 2,5-dihydroxyterephthalic acid, 2,2-dinitro-4,4-stilbenedicarboxylic acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 2-hydroxyterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 4,4,4''-s-triazine-2,4,6-triyl-tribenzoic acid(4,4,4''-s-triazine-2,4,6-triyltribenzoic acid), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-triscarboxyphenylethynylbenzene, It may be one or more selected from the group consisting of 2-methylimidazole and 2-aminoterephthalic acid, and may be one or more selected from the group consisting of benzene-1,4-dicarboxylic acid, 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 4,4'-biphenyldicarboxilic acid and 2-methylimidazole, but is not limited thereto.

[0120]

[0121] The metal-organic framework of the present invention may additionally have a ligand compound represented by the following chemical formula 1 bonded to it:

[0122] [Chemical Formula 1]

[0123]

[0124] Here,

[0125] n is an integer of 1 or 2, and

[0126] EDP ​​refers to a group containing an electron pair donor atom, and

[0127] L1 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, and a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms.

[0128] Specifically, the novel metal-organic framework having antioxidant activity of the present invention may be a metal-organic framework formed by the binding of a metal ion or metal cluster and an organic ligand, or a metal-organic framework formed by the binding of a metal ion or metal cluster and an organic ligand and a metal-organic framework combined with a ligand compound represented by Formula 1.

[0129] The ligand compound represented by the above chemical formula 1 may be a ligand compound represented by the following chemical formula 2 or chemical formula 3:

[0130] [Chemical Formula 2]

[0131]

[0132] [Chemical Formula 3]

[0133]

[0134] Here,

[0135] EDP ​​is as defined in Chemical Formula 1 above, and

[0136] m is an integer from 1 to 4, and

[0137] p is an integer of 0 or 1, and

[0138] L2 is selected from the group consisting of a single bond, a carbonyl group, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms.

[0139] X1 and X2 are identical or different from each other, and each is independently N or C(R3), and

[0140] R1 to R3 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 of It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0141] The above EDP is more specifically -NO 2, Groups comprising electron pair donor atoms capable of coordinate bonding with metal clusters may be selected from the group consisting of -NH2, -OH, -COOH, -OCH3 and mixtures thereof, but are not limited to the above examples, and any group comprising electron pair donor atoms capable of coordinate bonding with metal clusters may be selected.

[0142] The compound represented by the above chemical formula 2 may be selected from the group consisting of compounds represented by the following chemical formulas 4 to 11:

[0143] [Chemical Formula 4]

[0144]

[0145] [Chemical Formula 5]

[0146]

[0147] [Chemical Formula 6]

[0148]

[0149] [Chemical Formula 7]

[0150]

[0151] [Chemical Formula 8]

[0152]

[0153] [Chemical Formula 9]

[0154]

[0155] [Chemical Formula 10]

[0156]

[0157] [Chemical Formula 11]

[0158]

[0159] The compound represented by the above chemical formula 3 may be selected from the group consisting of compounds represented by the following chemical formulas 12 to 15:

[0160] [Chemical Formula 12]

[0161]

[0162] [Chemical Formula 13]

[0163]

[0164] [Chemical Formula 14]

[0165]

[0166] [Chemical Formula 15]

[0167]

[0168] As a ligand compound represented by Chemical Formula 1 as described above is additionally coordinated, in addition to the organic ligand exhibiting an antioxidant effect through decomposition as described above, the ligand compound represented by Chemical Formula 1 also acts in the same way to further enhance the antioxidant effect.

[0169] The above metal cluster is specifically a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, or Li + , Na + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 3+ , Ir 2+ , Ir + , Ni2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + It may include metal ions selected from the group consisting of

[0170] More specifically, the metal-organic framework may be selected from the group consisting of aluminum-based metal-organic frameworks, iron-based metal-organic frameworks, zirconium-based metal-organic frameworks, magnesium-based metal-organic frameworks, zinc-based metal-organic frameworks, and mixtures thereof.

[0171] The above metal-organic framework is UIO66, UIO66-NH2, UIO67, UIO67-NH2, PCN128, PCN222, PCN223, PCN224, MOF525, MOF545, MOF801, MOF808, MOF867, Al-MIL53, Al-MIL53-NH2, Al-MIL88, Al-MIL88-NH2, Al-MIL100, Al-MIL100-NH2, Al-MIL101, Al-MIL101-NH2, Al-MIL125, Al-MIL125-NH2, ZIF8, MgMOF74, MIL101-NH 2, MIL88-NH 2, Any metal-organic framework that can exhibit an antioxidant effect through the binding of metal ions, and whose antioxidant capacity is not reduced by light but is enhanced and / or maintained, may be selected from the group consisting of Fe-MIL53, Fe-MIL53-NH2, Fe-MIL88, Fe-MIL88-NH2, Fe-MIL100, Fe-MIL100-NH2, Fe-MIL101, Fe-MIL101-NH2, Fe-MIL125, Fe101-NH2, and Fe-MIL125-NH2, but is not limited to the above examples, may be used.

[0172] The metal-organic framework of the present invention, which is bonded to a metal ion, is characterized by maintaining its antioxidant capacity even after 24 hours or more and not decreasing due to light.

[0173] Although conventionally known metal-organic frameworks have been confirmed to have antioxidant capacity, it has been confirmed that the antioxidant effect decreases after 24 hours, indicating that they cannot maintain the antioxidant effect. On the other hand, the present invention has confirmed that a metal-organic framework with metal ions bound to it maintains the antioxidant effect even after 24 hours have elapsed.

[0174] When the metal-organic framework bound to metal ions of the present invention is exposed to light for 24 hours, the antioxidant capacity may increase by 0.1% to 30%, 0.1% to 29%, 0.1% to 28%, 0.1% to 27%, 0.1% to 26%, and 0.1% to 25%. The degree of increase in the antioxidant capacity was determined by measuring the antioxidant capacity of the metal-organic framework bound to metal ions before exposure to light, and then measuring the antioxidant capacity after exposure to light for 24 hours to confirm the degree of change in antioxidant capacity.

[0175] A cosmetic composition according to another embodiment of the present invention is characterized by comprising a metal-organic framework to which the metal ions described above are bonded, and can exhibit an antioxidant effect, said antioxidant effect can be maintained for 200 hours or more, and is characterized by not being reduced by light and maintaining and / or enhancing the antioxidant effect.

[0176] In addition to the above-described cosmetic composition, other ingredients commonly used in cosmetics may be incorporated into the cosmetic composition of the present invention as needed. Examples of such incorporated ingredients include oils, moisturizers, emollients, surfactants, organic and inorganic pigments, organic powders, UV absorbers, preservatives, disinfectants, antioxidants, pH adjusters, alcohols, colorants, fragrances, blood circulation promoters, cooling agents, decongestants, purified water, water-soluble vitamins, fat-soluble vitamins, high molecular weight peptides, high molecular weight polysaccharides, sphingolipids, etc.

[0177] The cosmetic composition of the present invention can be prepared in the form of emulsion formulations and solubilization formulations commonly used in the art.

[0178] In addition, the components included in the cosmetic composition of the present invention may include, in addition to the above components as active ingredients, components commonly used in cosmetic compositions, and may further include, for example, conventional auxiliary agents and carriers such as stabilizers, pigments, and natural fragrances.

[0179] Products to which the composition of the present invention can be added include, for example, cosmetics such as mist, skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nourishing lotion, massage cream, nourishing cream, sunscreen cream, moisture cream, hand cream, foundation, essence, nourishing essence, mask pack, pressed powder, loose powder, eyeshadow, etc., as well as soap, cleansing foam, cleansing lotion, cleansing cream, body lotion, and body cleanser.

[0180] In the case where the formulation of the present invention is a paste, cream, or gel, animal fibers, plant fibers, wax, paraffin, starch, tracanth, cellulose derivatives, polyethylene glycol, silicone, bentonite, silica, talc, or zinc oxide may be used as carrier components.

[0181] In the case where the formulation of the present invention is a powder or a spray, lactose, talc, silica, aluminum hydroxyl, calcium silicate, or polyamide powder may be used as a carrier component, and in particular, in the case of a spray, it may additionally include a propellant such as chlorofluorohydrocarbon, propane, butane, or dimethyl ether.

[0182] In the case where the formulation of the present invention is a solution or emulsion, a solvent, a solvating agent, or an emulsifying agent is used as a carrier component, such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol oil, glycerol aliphatic ester, polyethylene glycol, or fatty acid ester of sorbitan.

[0183] In the case where the formulation of the present invention is a suspension, liquid diluents such as water, ethanol, or propylene glycol, suspending agents such as ethoxylated isostearyl alcohol, polyoxyethylene sorbitol ester, and polyoxyethylene sorbitan ester, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar, or tracant may be used as carrier components.

[0184] As described above, the cosmetic composition of the present invention is characterized by comprising the metal-organic framework bound to the metal ion and exhibiting an excellent antioxidant maintenance effect. To enhance the antioxidant effect, the content included in the cosmetic composition may be within the content range of the constituent components typically included in cosmetic compositions, and may be included in small or large amounts to control the antioxidant capacity. Furthermore, the content range of the metal-organic framework bound to the metal ion included in the cosmetic composition is not limited. That is, the content range of the metal-organic framework bound to the metal ion may be appropriately adjusted and included according to the formulation, use, effect, etc. of the cosmetic.

[0185] Preparation Example 1

[0186] Preparation of metal-organic frameworks bonded with metal ions

[0187] Zn / Al-MIL-101-NH2 synthesis

[0188] 60 mL of DMF was weighed. 724 mg of aluminum chloride was weighed and dissolved in DMF. 516 mg of 2-aminoterephthalic acid was weighed and dissolved in the DMF solution, and this was added to a synthesizer. The synthesizer reacted for 16 hours under a temperature condition of 90 ℃.

[0189] A pale yellow suspension was obtained and centrifuged at 15,000 rpm; the supernatant was discarded, and the product collected in the lower layer was obtained. 35 mL of DMF was added to the product to resuspend it, and after vortex mixing for 5 minutes, washing was repeated three times by centrifuging at 15,000 rpm to re-sediment. Particles were obtained by washing three times with 35 mL of ethanol each. Al-mil-101-NH2 powder was obtained by drying in a drying oven at 100°C for 6 hours. The Al-mil-101-NH2 was subjected to reduced pressure treatment in a vacuum oven at 200°C for 24 hours.

[0190] 500 mg of zinc acetate was weighed and dissolved in 10 mL of ethanol. 1 g of the above Al-MIL-101-NH2 was weighed and added to 10 mL of the zinc acetate solution, and stirred for 48 hours. Afterward, the mixture was centrifuged at 15,000 rpm and allowed to settle to obtain the particles collected in the lower layer. 35 mL of ethanol was added to resuspend the mixture, and after vortex mixing for 5 minutes, the washing process of centrifuging at 15,000 rpm and allowing to settle again was repeated 3 times. Subsequently, the mixture was dried in an oven at 100°C for 6 hours to obtain a Zn / Al-MIL-101-NH2 powder sample.

[0191] Experimental Example 1

[0192] Synthesis result analysis

[0193] To measure using a Scanning Electron Microscope (SEM), a powder sample was placed in a 2 mg to 3 mg Eppen tube, 100 µl of ethanol was added, and bath sonification was performed. Subsequently, 10 µl was spot-dried onto a silicon wafer and dried in an 80°C oven. The silicon wafer with the dried sample was then attached to the SEM mount using carbon tape and transferred to the SEM instrument to measure images (Company: Zeiss / Model: ULTRA PLUS).

[0194] Next, for X-ray diffraction (XRD) measurement, the powder sample was carefully placed on the XRD sample holder and compressed by pressing it with a glass slide glass with appropriate force. Afterward, all powder scattered around the sample holder was carefully removed, the sample holder was transferred to the equipment and set up, and measurements were performed in the range of 2°C to 30°C (Company: Bruker / Model: D2 phaser).

[0195] Next, for N2 adsorption isotherms and BET specific surface area-pore measurements, approximately 40 mg of a completely dried sample was prepared and carefully placed into a glass sampler using a glass funnel. All powder adhering to the area around the glass tube and the sample container at the bottom was removed. Subsequently, the top filter cap was attached, and degassing was performed in a pretreatment apparatus under vacuum and heat treatment at 120°C for 12 hours. The weight of the pretreated sample was measured using a microbalance, and the weight of the intact sample was calculated by subtracting the weight of the previously measured empty cell. The glass sampler was mounted on the N2 adsorption-desorption apparatus, and measurements were performed (Company Name: MICROTAAC / Model Name: BELSORP MINI X).

[0196] The schematic diagram of the above Zn / Al-MIL-101-NH2 is as shown in Fig. 1. As shown in the schematic diagram, Zn / Al-MIL-101-NH2 is Al-MIL-101-NH2 It is a combination of Zn ions.

[0197] Scanning electron microscope (SEM) observation results for the above Zn / Al-MIL-101-NH2 are shown in Fig. 2. In addition, X-ray diffraction analysis results are shown in Fig. 3, confirming that the prepared particles were synthesized with the crystal structure of Zn / Al-MIL-101-NH2. Furthermore, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption are shown in Fig. 4. The specific surface area of ​​the Zn / Al-MIL-101-NH2 particles is 518.6 m². 2 / g is.

[0198] Comparing the above analysis results, it can be confirmed that the specific surface area of ​​the metal-organic framework varies significantly depending on the binding of Zn ions. In addition, to more clearly confirm the binding of Zn ions to Al-MIL-101-NH2, ICP-AES analysis was performed on Zn / Al-MIL-101-NH2 to analyze the concentrations of Zn and Al.

[0199] The specifications of the analytical instrument for ICP-AES analysis are as follows:

[0200] Model: OPTIMA 8300, Perkin-Elmer (USA)

[0201] Source: Argon plasma(6000K)

[0202] Spectral range: 167-782nm

[0203] Resolution: Better than 0.006nm at 200nm

[0204] Detection limit: 10 ppb - several hundred ppb

[0205] The analysis results are as shown in Table 1 below:

[0206] ZnAlZnAl144810.19 ppm40087.67ppm

[0207] (Unit ppm=mg / kg)

[0208] According to the above analysis results, it was confirmed that Zn / Al-MIL-101-NH2 contains Zn as well as Al.

[0209]

[0210] Experimental Example 2

[0211] Antioxidant capacity evaluation

[0212] Positive control: 10 mg of ascorbic acid (product number; A4544, company name: sigma) was dissolved in 10 ml of water to prepare a 1000 ppm sample, and then redidicated to 1 / 10 to prepare a final 100 ppm sample. Test group (Zn / Al-MIL-101-NH2) 10 mg was dissolved in 10 ml of water to prepare a 1000 ppm sample.

[0213] For the measurement of antioxidant capacity, 150 μL of Ultra Pure Water was added to 50 μL each of the positive control, control, and test groups, and this was used as a blank value. 150 μL of DPPH reagent (2,2-diphenyl-1-picrylhydrazyl) 0.2 mM solution (Product No.: D9132, Manufacturer: Merck) was added to 50 μL each of the positive control, control, and test groups, and the reaction was carried out for 30 minutes at room temperature in the dark.

[0214] Absorbance was measured at 520 nm using a BioTek Synergy HTX multimode reader. DPPH antioxidant activity (radical scavenging activity (%)) was calculated using the following formula.

[0215] Scavenging activity(%) = [1-(ABS Sample -ABS Sampleblank / ABS Control -ABS Controlblank )] × 100

[0216] ABS Sample: Absorbance of wells into which 150 μL of DPPH 0.2 mM solution was added to 50 μL each of the positive control, control, and test groups

[0217] ABS Sampleblank : Absorbance of wells to which 150 μL of Ultra Pure Water solution was added to 50 μL each of the positive control, control, and test groups

[0218] ABS Control : Absorbance of a well into which 150 μL of DPPH 0.2 mM solution was added to Ultra Pure Water

[0219] ABS Controlblank : Absorbance of the well with 200 μL of Ultra Pure Water added

[0220]

[0221] Whether antioxidant capacity was maintained for 24 hours for the above control and test groups was verified, and the results are as shown in Table 2 below:

[0222] Concentration (ppm) 0 hours 24 hours Antioxidant power (%) Zn / Al-MIL-101-NH2100039.3246.59

[0223] According to the above test results, the test group not only demonstrated superior antioxidant effects compared to the control group, but it was also confirmed that the test group showed an 18.5% increase after 24 hours. This implies that the Zn-ion-bound metal-organic framework can sustain its antioxidant effect for more than 24 hours. Additionally, to verify changes in antioxidant capacity due to sunlight, the samples were exposed to sunlight; measurements were taken separately before exposure (0 hours) and after 24 hours of exposure, and the changes in antioxidant capacity were assessed. The results are shown in Table 3 below:

[0224] Concentration (ppm) 0 Hour 24 Hour Change Rate Antioxidant Power (%) Ascorbic Acid 100 82.0 10 100 0.0% Decrease Zn / Al-MIL-101-NH2 100 03 9.3 24 6.5 918.5% Increase 100 15.0 11 6.0 87.13% Increase

[0225] According to the above test results, there is a difference in the absolute antioxidant power of the metal-organic framework of the present invention compared to vitamin C, but as is known, vitamin C was found to have an antioxidant power of 0% when exposed to sunlight for 24 hours.

[0226] On the other hand, it was confirmed that the antioxidant capacity of the Zn / Al-MIL-101-NH2 of the present invention increased by 18.52% and 7.13% when exposed to sunlight for 24 hours. This implies that the antioxidant capacity of the Zn / Al-MIL-101-NH2 of the present invention is not altered by sunlight.

[0227]

[0228] Preparation Example 2

[0229] Preparation of metal-organic frameworks bonded with metal ions

[0230] UIO66 Synthetic

[0231] 4.08 g of terephthalic acid, 6.36 g of ZrCl4 (Zirconium(IV) chloride), and 11.2 g of benzoic acid were added to 250 ml of DMF, dissolved, and reacted at 125°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, and dried at 80°C to obtain a powder.

[0232] UIO67 synthesis

[0233] 720 mg of BPDC (4,4'-Biphenyldicarboxylic acid) and 690 mg of ZrCl4 (Zirconium(IV) chloride) were added to 80 ml of DMF and dissolved, and the mixture was reacted at 95°C for 17 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, and dried at 80°C to obtain a powder.

[0234] UIO66NH2 synthesis

[0235] 330 mg of BDC-NH2(2-Aminoterephthalic acid), 360 mg of ZrCl4 (Zirconium(IV) chloride), and 11.4 g of benzoic acid were added to 60 ml of DMF, dissolved, and reacted at 120°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, and dried at 80°C to obtain a powder.

[0236] MIL101NH2(Al) synthesis

[0237] 4.344 g of AlCl3 (Aluminum chloride) and 1.632 g of BDC-NH2 (2-Aminoterephthalic acid) were added to 120 ml of DMF and dissolved, and the mixture was reacted at 110°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, respectively, and dried at 80°C to obtain a powder.

[0238] MIL101NH2(Fe) synthesis

[0239] 135 mg of BDC-NH2(2-Aminoterephthalic acid) and 405 mg of FeCl3*6H2O (Iron(III) chloride hexahydrate) were added to 40 ml of DMF and dissolved, and the mixture was reacted at 110°C for 12 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, and dried at 80°C to obtain a powder.

[0240] MIL88NH2(Fe) synthesis

[0241] 1.39 g of BDC-NH2(2-Aminoterephthalic acid) and 2.24 g of FeCl3*6H2O (Iron(III) chloride hexahydrate) were added to 60 ml of DMF and dissolved, then 0.9 ml of acetic acid was added and stirred, and the mixture was reacted at 120°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, respectively, and dried at 80°C to obtain a powder.

[0242] MgMOF74 synthesis

[0243] 465 mg of BDC-OH (2,5-dihydroxybenzene carboxylic acid) and 1.99 g of Mg(NO3)*6H2O (Magnesium nitrate hexahydrate) were added to 62 ml of DMF and dissolved, and the mixture was reacted at 125°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, respectively, and dried at 80°C to obtain a powder.

[0244] ZIF8 synthesis

[0245] 7.2 g of zinc acetate was dissolved in 20 ml of distilled water, and 26.88 g of 2-methylimidazole was dissolved in 20 ml of distilled water. The two solutions were then mixed and reacted at 40°C for 1 hour. Afterward, the synthesized particles were washed three times each with distilled water and ethanol, and dried at 80°C to obtain a powder.

[0246] MOF808 synthesis

[0247] 1.78 g of 1,3,5-BTC (1,3,5-Benzenetricarboxylic acid) and 2.59 g of ZrOCl2 (Zirconyl chloride) were added to 51.2 ml of DMF and dissolved, then 53.2 ml of formic acid was added and stirred, and the mixture was reacted at 100°C for 36 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, respectively, and dried at 80°C to obtain a powder.

[0248] MOF525 synthesis

[0249] 6.75 g of benzoic acid was added to 60 ml of DMF and dissolved, then 705 mg of TCPP (Tetrakis(4-carboxyphenyl)porphyrin) and 1.57 g of ZrOCl2 (Zirconyl chloride) were added and stirred, and the mixture was reacted at 100°C for 24 hours. Afterward, the synthesized particles were washed three times each with DMF and ethanol, and dried at 80°C to obtain a powder.

[0250] UIO67-ABA synthesis

[0251] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. The powder from which the residual solution had been removed was mixed with ABA (3-Aminobenzyl alcohol) at a molar ratio of 1:50 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was dried at 80°C to obtain the powder.

[0252] UIO67-ALA synthesis

[0253] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. ALA (5-aminolevulinic acid) was dissolved in DMSO at a concentration of 59 mg / ml. The UIO67 with the residual solution removed and ALA were mixed in a molar ratio of 1:5 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0254] UIO67-AIA Synthesis

[0255] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. AIA (5-Aminoisophthalic acid) was dissolved in DMSO at a concentration of 51 mg / ml. The UIO67 with the residual solution removed and AIA were mixed in a molar ratio of 1:20 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0256] UIO67-PTA synthesis

[0257] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours in a vacuum environment at 150°C. The UIO67 from which the residual solution had been removed and PTA (p-toluamide) were mixed in a molar ratio of 1:5 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0258] UIO67-ABZ synthesis

[0259] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. ABZ (3-Aminobenzoic acid) was dissolved in DMSO at a concentration of 215 mg / ml. The UIO67 with the residual solution removed and ABZ were mixed in a molar ratio of 1:30 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0260] UIO67-GAB synthesis

[0261] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. A GAB (γ-Aminobutyric acid) solution with a concentration of 9 mg / ml was prepared using methanol. UIO67, from which the residual solution had been removed, was suspended in 8 ml of the GAB solution such that the molar ratio of UIO67 to GAB was 1:5, and the mixture was left at room temperature for 16 hours. The synthesized particles were washed three times each with ethanol. After removing the ethanol, the powder was obtained by drying at 80°C.

[0262] UIO67-LS synthesis

[0263] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. An LS solution with a concentration of 100 mg / ml was prepared using ethanol. UIO67 was suspended in 3 ml of the LS solution such that the molar ratio of the residual-removed UIO67 to LS was 1:25, and the suspension was left at room temperature for 16 hours. The synthesized particles were washed three times each using ethanol. The powder was obtained by drying at 80°C.

[0264] UIO67-MNA synthesis

[0265] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. The UIO67 from which the residual solution had been removed and MNA (4-Methyl-3-nitroaniline) were mixed in a molar ratio of 1:5 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was dried at 80°C.

[0266] UIO67-APD synthesis

[0267] The residual solution within the pores of the synthesized UIO67 powder was removed by vacuuming at 150°C for 8 hours. APD (2-Aminopyridine) was dissolved in DMSO at a concentration of 50 mg / ml. The UIO67 with the residual solution removed and APD were mixed in a molar ratio of 1:15 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0268] UIO67-DAT synthesis

[0269] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. The powder from which the residual solution had been removed was mixed with DAT (3,4-Diaminotoluene) at a molar ratio of 1:50 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was dried at 80°C to obtain the powder.

[0270] UIO67-MB synthesis

[0271] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. The UIO67 from which the residual solution had been removed and MB (2-methylbutylamine) were mixed at a molar ratio of 1:25 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0272] UIO67-MN synthesis

[0273] The synthesized UIO67 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. The UIO67 from which the residual solution had been removed and MN (2-Methoxy-4-nitroaniline) were mixed in a molar ratio of 1:5 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. Subsequently, the synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0274] UIO66-AIA Synthesis

[0275] The residual solution within the pores of the synthesized UIO66 powder was removed by vacuuming at 150°C for 8 hours. AIA (5-Aminoisophthalic acid) was dissolved in DMSO at a concentration of 20 mg / ml. The UIO66 with the residual solution removed and AIA were mixed in a molar ratio of 1:25 and suspended in 50 ml of toluene. The solution was placed in a round flask, the flask was connected to a reflux condenser, and stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0276] UIO66-ABZ synthesis

[0277] The synthesized UIO66 powder was subjected to removing residual solution from within the pores for 8 hours under a vacuum at 150°C. ABZ (3-Aminobenzoic acid) was dissolved in DMSO at a concentration of 80 mg / ml. The UIO66 with the residual solution removed and ABZ were mixed in a molar ratio of 1:25 and suspended in 50 ml of toluene. The solution was placed in a round flask, connected to a reflux condenser, and stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0278] MIL101NH2(Al)-AIA synthesis

[0279] The residual solution within the pores of the synthesized MIL101NH2(Al) powder was removed for 8 hours under a vacuum at 150°C. AIA (5-Aminoisophthalic acid) was dissolved in DMSO at a concentration of 30 mg / ml. The MIL101NH2(Al) from which the residual solution had been removed and AIA were mixed in a molar ratio of 1:10 and suspended in 30 ml of toluene. The solution was placed in a round flask, and the flask was connected to a reflux condenser. Subsequently, the mixture was stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0280] MIL101NH2(Al)-ABZ synthesis

[0281] The residual solution within the pores of the synthesized MIL101NH2(Al) powder was removed for 8 hours under a vacuum at 150°C. ABZ (3-Aminobenzoic acid) was dissolved in DMSO at a concentration of 200 mg / ml. The MIL101NH2(Al) from which the residual solution had been removed and ABZ were mixed in a molar ratio of 1:20 and suspended in 30 ml of toluene. The solution was placed in a round flask, and the flask was connected to a reflux condenser. Subsequently, the mixture was stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0282] MgMOF74-AIA synthesis

[0283] The residual solution within the pores of the synthesized MgMOF74 powder was removed by vacuuming at 150°C for 8 hours. AIA (5-Aminoisophthalic acid) was dissolved in DMSO at a concentration of 60 mg / ml. The MgMOF74 from which the residual solution had been removed and AIA were mixed in a molar ratio of 1:10 and suspended in 30 ml of toluene. The solution was placed in a round flask, and the flask was connected to a reflux condenser. Subsequently, the mixture was stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0284] MgMOF74-ABZ synthesis

[0285] The residual solution within the pores of the synthesized MgMOF74 powder was removed by vacuuming at 150°C for 8 hours. ABZ (3-Aminobenzoic acid) was dissolved in DMSO at a concentration of 200 mg / ml. The MgMOF74 from which the residual solution had been removed and ABZ were mixed in a molar ratio of 1:10 and suspended in 30 ml of toluene. The solution was placed in a round flask, and the flask was connected to a reflux condenser. Subsequently, the mixture was stirred at 100°C for 6 hours. The synthesized particles were washed three times each with toluene and ethanol, respectively, and subjected to ethanol substitution for 3 days. After removing the ethanol, the powder was obtained by drying at 80°C.

[0286]

[0287] Experimental results

[0288] Analysis of synthesis results and evaluation of cytotoxicity

[0289] To measure using a Scanning Electron Microscope (SEM), a powder sample was placed in a 2 mg to 3 mg Eppen tube, 100 µl of ethanol was added, and bath sonification was performed. Subsequently, 10 µl was spot-dried onto a silicon wafer and dried in an 80°C oven. The silicon wafer with the dried sample was then attached to the SEM mount using carbon tape and transferred to the SEM instrument to measure images (Company: Zeiss / Model: Gemini 560).

[0290] Next, for X-ray diffraction (XRD) measurement, the powder sample was carefully placed on the XRD sample holder and compressed by pressing it with a glass slide glass with appropriate force. Afterward, all powder scattered around the sample holder was carefully removed, the sample holder was transferred to the equipment and set up, and measurements were performed in the range of 2°C to 30°C (Company: Rigaku / Model: JD / SmartLab).

[0291] Next, for N2 adsorption isotherms and BET specific surface area-pore measurements, approximately 40 mg of a completely dried sample was prepared and carefully placed into a glass sampler using a glass funnel. All powder adhering to the area around the glass tube and the sample container at the bottom was removed. Subsequently, the top filter cap was attached, and degassing was performed in a pretreatment apparatus under vacuum and heat treatment at 120°C for 12 hours. The weight of the pretreated sample was measured using a microbalance, and the weight of the intact sample was calculated by subtracting the weight of the previously measured empty cell. The glass sampler was mounted on the N2 adsorption-desorption apparatus, and measurements were performed (Company Name: MICROTAAC / Model Name: BELSORP MINI X).

[0292] L929 (mouse fibroblasts) were seeded into a 96-well plate at a density of 10,000 cells / well and cultured for 24 hours in a 37°C, 5% CO2 incubator. After 24 hours, the existing medium was removed from each well, and test solutions were prepared by suspending the particles to be tested in the medium at concentrations of 100, 50, 25, 10, 5, and 1 µg / ml. 100 µl of these solutions were then added to each well. After incubating for 24 hours in a 37°C, 5% CO2 incubator, the medium was removed and the cells were washed three times with PBS. 10% EZ-cytox medium was added to each well and incubated for 1 hour. Absorbance at 450 nm and 600 nm was measured using a microplate reader to compare cell viability with that of the control group.

[0293]

[0294] Figure 5 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO-66. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO-66, and the specific surface area is 1423.8 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0295] Figure 6 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO-67. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO-67, and the specific surface area is 2192.8 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0296] Figure 7 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO66-NH2. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO66-NH2, and the specific surface area is 1307.2 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0297] Figure 8 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the MIL101NH2(Al). Based on the analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MIL101NH2(Al), and the specific surface area is 989.93 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0298] Figure 9 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above MIL88-NH2. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MIL88-NH2, and the specific surface area is 233.5 m² 2 It was confirmed that it is / g and has no cytotoxicity.

[0299] Figure 10 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above MgMOF74. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MgMOF74, and the specific surface area is 1358.8 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0300] Figure 11 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above ZIF8. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of ZIF8, and the specific surface area is 1757.4 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0301] Figure 12 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above MIL101NH2(Fe). Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MIL101NH2(Fe), and the specific surface area is 836.33 m² 2 It was confirmed that it is / g and has no cytotoxicity.

[0302] Figure 13 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the MOF-525. Based on the analysis results, it was confirmed that the prepared particles were synthesized with the crystal structure of MOF-525, and the specific surface area is 1356.3 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0303] Figure 14 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the MOF-808. Based on the analysis results, it was confirmed that the prepared particles were synthesized with the crystal structure of MOF-808, and the specific surface area is 1582.4 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0304] Figure 15 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-ABA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-ABA, and the specific surface area is 2736.1 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0305] Figure 17 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-ALA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-ALA, and the specific surface area is 1167 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0306] Figure 18 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-AIA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-AIA, and the specific surface area is 1134 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0307] Figure 19 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-PTA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-PTA, and the specific surface area is 2507.8 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0308] Figure 20 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-ABZ. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-ABZ, and the specific surface area is 1581 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0309] Figure 21 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-GAB. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-GAB, and the specific surface area is 1494.8 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0310] Figure 22 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-LS. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-LS, and the specific surface area is 164.1 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0311] Figure 23 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-MNA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-MNA, and the specific surface area is 3088.4 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0312] Figure 24 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-APD. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-APD, and the specific surface area is 1750.5 m² 2 It was confirmed that it is / g and has no cytotoxicity.

[0313] Figure 25 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-DAT. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-DAT, and the specific surface area is 2756.3 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0314] Figure 26 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-MB. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-MB, and the specific surface area is 2541.5 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0315] Figure 27 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO67-MN. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO67-MN, and the specific surface area is 2457 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0316] Figure 28 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO66-AIA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO66-AIA, and the specific surface area is 1246.5 m² 2 It was confirmed that it is / g and has no cytotoxicity.

[0317] Figure 29 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above UIO66-ABZ. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of UIO66-ABZ, and the specific surface area is 1501.9 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0318] Figure 30 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the MIL101NH2(Al)-ABZ. Based on the analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MIL101NH2(Al)-ABZ, and the specific surface area was 190.7 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0319] Figure 31 shows the scanning electron microscope (SEM) observation results, X-ray diffraction (XD) analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the MIL101NH2(Al)-AIA. Based on the analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MIL101NH2(Al)-AIA, and the specific surface area is 163.2 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0320] Figure 32 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above MgMOF74-ABZ. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MgMOF74-ABZ, and the specific surface area is 592.46 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0321] Figure 33 shows the scanning electron microscope (SEM) observation results, X-ray diffraction analysis results, BET (Brunauer-Emmett-Teller) analysis results via N2 adsorption, and cytotoxicity evaluation results for the above MgMOF74-AIA. Based on the above analysis results, it was confirmed that the prepared particles were synthesized having the crystal structure of MgMOF74-ABZ, and the specific surface area is 428.41 m². 2 It was confirmed that it is / g and has no cytotoxicity.

[0322]

[0323] Experimental method

[0324] Antioxidant capacity measurement

[0325] ORAC assay experimental method

[0326] A 75 mM phosphate buffer (pH 7.4) was prepared using potassium phosphate monobasic (KH2PO4) and potassium phosphate dibasic (K2HPO4). A 4 nM fluorescein working solution was prepared by diluting the fluorescein sodium salt reagent with 75 mM phosphate buffer. A 180 mM AAPH solution was prepared by diluting the AAPH (2,2'-azobis(2-methylpropionamidine) dihydrochloride) reagent with 75 mM phosphate buffer.

[0327] The sample to be used in the experiment was prepared by suspending it at a certain concentration using 75 mM Phosphate buffer.

[0328] 25 µl of sample was placed in each well of a 96-well plate (Side black, Bottom transparent), and 150 µl of 4 nM Fluorescein working solution was added. In the blank wells, 25 µl of 75 mM phosphate buffer and 150 µl of 4 nM Fluorescein working solution were added.

[0329] A 96-well plate was placed in a plate reader and incubated at 37°C for 30 minutes. 25 µl of 180 mM AAPH solution was added to each well, and the plate was shaken for 10 seconds. Kinetics were measured via bottom reads at 60-second intervals for 70 minutes.

[0330] Kinetic measurement conditions

[0331] Fluorescein / Kinetic mode / Bottom-read

[0332] Excitation: 485 nm / 20 nm bandpass

[0333] Emission: 528 nm / 20 nm bandpass

[0334] 71 measurements every 60 seconds

[0335]

[0336] The method for calculating antioxidant capacity is as follows.

[0337]

[0338] R1: Initial fluorescence value immediately after the start of the reaction

[0339] Rn: Fluorescence value at the last measurement after the start of the reaction

[0340]

[0341] The fluorescence value at each time point was normalized by dividing it by the initial fluorescence value, and then the result was cumulatively summed over all time points to obtain the AUC (Area Approximation) of the corresponding well.

[0342] The AUC of the sample was calculated in the sample well in the same manner as above.

[0343] The AUC of the blank was calculated by performing the same calculation for the blank (control group without antioxidants) well.

[0344] The Net AUC was calculated by subtracting the AUC value of the blank from the AUC of the sample, and this was used as an indicator of the antioxidant capacity of the sample.

[0345] After plotting the Net AUC of each sample as a concentration-dependent graph, linear regression was applied to each sample curve.

[0346] The results of verifying the slope of the graph of the Net AUC versus concentration for each sample using the above calculation method are as shown in Table 4 and Figures 34 to 40 below:

[0347] MOF slopeUIO67ABA0.0047UIO67ALA0.004UIO67AIA0.022UIO67PTA0.0036UIO67ABZ0.0444UIO67GAB0.001UIO67LS0.001 2UIO67MNA0.0023UIO67APD0.0018UIO67DAT0.0043UIO67MB0.0017UIO67MN0.0014UIO66AIA0.0178UIO66ABZ0.1337MIL 101NH2(Al)-AIA0.0498MIL101NH2(Al)-ABZ0.0373MgMOF74-AIA1.5567MgMOF74-ABZ0.823UIO66-UIO670.0013UIO66NH 20.0344MIL101NH2(Al)0.0269MIL88-NH20.1136MgMOF741.1188ZIF80.0344MIL101NH2(Fe)0.057MOF5250.013MOF808-

[0348] According to Table 4 and Figures 34 to 40 above, it was confirmed that UIO66 and MOF808 do not have antioxidant activity, while other MOFs have antioxidant effects. In particular, regarding UIO66, it was confirmed that an antioxidant effect was observed in the case of a metal-organic framework in which a ligand compound was coordinately bonded to UIO66.

[0349]

[0350] Additionally, the antioxidant capacity of the organic ligand compounds constituting the metal-organic framework was evaluated using the same method as the experiment evaluating the antioxidant capacity of the metal-organic framework. The results are shown in Table 5, Figure 41, and Figure 42 below:

[0351] MOF Ligand Gradient BDC 0.0009 BPDC 0.0022 BDC-NH2 0.2431 BDC-OH 8.6892-IM 0.137

[0352] According to the experimental results above, it was confirmed that BDC (1,4-benzenedicarboxylic acid), BPDC (4,4'-biphenyldicarboxylic acid), BDC-NH2 (2-aminoterephthalic acid), BDC-OH (2-hydroxyterephthalic acid), and 2-IM (2-methylimidazole) all have antioxidant effects. This implies that organic ligand compounds constituting the organo-metal framework can exhibit antioxidant effects, and that antioxidant effects are manifested through this.

[0353] Subsequently, through experiments, the sustained effect of the antioxidant capacity of the organo-metal framework and organic ligand compound of the present invention was confirmed.

[0354] The experimental method is as follows:

[0355] The sample was suspended to a constant concentration using 75 mM phosphate buffer. The suspension was dispensed into 1 ml tubes and left exposed to light at room temperature. Samples were collected immediately after suspension (t=0h) and after 200 hours (t=200h), and antioxidant capacity was measured using the ORAC assay. Sample concentration-net AUC graphs were plotted at t=0h and t=200h to determine the slope, and the residual activity rate was calculated by analyzing the change in slope.

[0356] (Eq. 4)

[0357] In the experiment to measure the self-antioxidant capacity of organic ligands, the experiment was conducted using the same experimental method as above, but instead of 200 hours of suspension (t=200h), a sample was taken after 24 hours of suspension (t=24h) and calculated by substituting it into the same equation as above.

[0358]

[0359] The experimental results regarding the sustained antioxidant effect of the metal-organic framework of the present invention are as shown in Table 6 below:

[0360] Gradient Residual Activity (%) MOF 0 Time 200 Time UIO66NH2 0.03440.0434126.2 UIO67ABZ 0.04460.042795.7 UIO66ABZ 0.06690.05683.7 MIL 101NH2(Al) 0.02690.0927344.6 Ascorbic Acid 0.0640.00264.1

[0361] According to the above experimental results, ascorbic acid, a vitamin C known for its excellent antioxidant effect, was tested for 200 hours to see if its antioxidant effect persisted. However, after 200 hours, the residual antioxidant activity was found to be 4.1%, which is a decrease of 95.9%.

[0362] On the other hand, it was confirmed that the metal-organic framework of the present invention showed a very small decrease even after 200 hours, and rather, the antioxidant activity increased even after 200 hours.

[0363] To identify the reasons why the antioxidant effect was nearly maintained or increased over these 200 hours, the change in antioxidant capacity over 24 hours for organic ligand compounds included in the metal-organic framework was measured. The experimental results are shown in Table 7 below:

[0364] Gradient Residual Activity (%) MOF0 Time 24 Hours BDC-NH2 0.203 20.202 799.7 BDC-OH 6.68 296.37 2395.3

[0365] As shown in Table 7 above, it was confirmed that there was no significant change in the antioxidant activity of the organic ligand compound even after 24 hours.

[0366]

[0367] Accordingly, to additionally confirm whether the coordinately bonded organic ligand within the metal-organic framework of the present invention is released, the following experiment was conducted.

[0368] A measured amount of the MIL101NH2(Al) sample was weighed and suspended in pH 7.4 PBS. 2 ml of the suspension was placed in a dialysis tube (MWCO 3.5 kDa) and sealed with a clip. 18 ml of pH 7.4 PBS was placed in a glass vial, the dialysis tube containing the suspension was placed inside, and the vial was left at room temperature. At set intervals, 5 ml of the solution was taken and 5 ml of fresh PBS was added, and this process was repeated. The ligand release amount of the solution taken at each time interval was measured using HPLC:

[0369] HPLC measurement conditions

[0370] Column: Newcrom R1 (3.2 x 100 mm, 3 um, 100 ℃)

[0371] Column temperature: 35 ℃

[0372] Wavelength: 250 nm

[0373] Flow rate: 1 ml / min

[0374] Mobile phase: 0.1% phosphoric acid in DW: Acetonitrile = 84:16

[0375]

[0376] The experimental results are as shown in Fig. 42. According to Fig. 42, it can be confirmed that BDC-NH2 of MIL101NH2(Al) is released over time.

[0377] This, together with the results of Tables 6 and 7 above, makes it possible to explain the antioxidant effect of the metal-organic framework of the present invention. That is, the metal-organic framework of the present invention exhibits an antioxidant effect through organic ligands, and the organic ligands coordinately bonded within the metal-organic framework break their bonds and are released, thereby exhibiting antioxidant activity. This implies that antioxidant activity resulting from the release of organic ligands appears after more than 200 hours.

[0378]

[0379] Additionally, to evaluate the excellence of the antioxidant effect of the metal-organic framework of the present invention, it was determined whether the antioxidant effect is affected by ultraviolet irradiation. This is intended to determine whether the antioxidant effect is reduced or maintained when the metal-organic framework of the present invention is included in various cosmetic compositions and applied to the skin, upon exposure to ultraviolet irradiation.

[0380] The experimental method is specifically as follows:

[0381] Samples were prepared at least three concentrations using 75 mM phosphate buffer and placed in glass vials. A UV lamp (100W) emitting UVA and UVB was installed at a distance of approximately 30 cm from the samples, and the samples were irradiated with UV for 6 hours and 24 hours. After 6 or 24 hours of UV irradiation, samples were collected, and ORAC assay experiments were performed.

[0382] The experimental results are shown in Figures 43 to 47. Using Trolox and Ascorbic acid, which are known to have antioxidant effects, as control groups, the antioxidant effects at 0, 6, and 24 hours were confirmed; however, as shown in Figure 43, the antioxidant effects of Trolox and Ascorbic acid decreased due to ultraviolet radiation as time progressed. On the other hand, it was confirmed that the metal-organic framework of the present invention actually showed a greater antioxidant effect at 6 and 24 hours after ultraviolet irradiation. As described above, these experimental results indicate that the organic ligands coordinated within the metal-organic framework are broken and released by ultraviolet radiation, thereby increasing antioxidant activity.

[0383]

[0384] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

[0385] The present invention relates to a novel metal-organic framework having antioxidant activity and an antioxidant cosmetic composition containing the same.

Claims

1. Metal ions or metal clusters; and It comprises at least one organic ligand that forms a metal-organic framework (MOF) by forming a bond with the metal ion, and Exhibiting an antioxidant effect by the above-mentioned organic ligand Novel metal-organic framework.

2. In Paragraph 1, The above metal-organic framework has a ligand compound represented by the following chemical formula 1 additionally bonded to it. Novel Metal-Organic Framework: [Chemical Formula 1] Here, n is an integer of 1 or 2, and EDP ​​refers to a group containing an electron pair donor atom, and L1 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, and a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms.

3. In Paragraph 2, The ligand compound represented by the above chemical formula 1 is a ligand compound represented by the following chemical formula 2 or chemical formula 3. Novel Metal-Organic Framework: [Chemical Formula 2] [Chemical Formula 3] Here, The EDP is as defined in Paragraph 2, and m is an integer from 1 to 4, and p is an integer of 0 or 1, and L2 is selected from the group consisting of a single bond, a carbonyl group, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms. X1 and X2 are identical or different from each other, and each is independently N or C(R3), and R1 to R3 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 of It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

4. In Paragraph 1, The above metal cluster comprises a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Novel metal-organic framework.

5. In Paragraph 1, 상기 금속 이온은 Li + In + , Mg 2+ , Ca 2+ Mr. 2+ , Ba 2+ , Sc 3+ Y 3+ Ti 4+ Zr 4+ , Hf 4+ V 4+ V 3+ V 2+ , Nb 3+ Ta 3+ Cr 3+ Mo 3+ W 3+ , Mn 3+ , Mn 2+ Re 3+ Re 2+ , Faith 3+ , Faith 2+ , Ru 3+ Ru 2+ , You 3+ , You 2+ Co 3+ Co 2+ Rh 2+ Rh + Go 3+ Go 2+ Go + Ni 2+ Ni + , Pd 2+ , Pd + , PT 2+ , PT + , Cu 2+ , Cu + , Ag + Au + Zn 2+ CD 2+ Hg 2+ Al 3+ Ga 3+ In 3+ , Tl 3+ Yes 4+ Yes 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + Selected from a group consisting of Novel metal-organic framework.

6. In Paragraph 1, The metal-organic framework is selected from the group consisting of aluminum-based metal-organic frameworks, iron-based metal-organic frameworks, zirconium-based metal-organic frameworks, magnesium-based metal-organic frameworks, zinc-based metal-organic frameworks, and mixtures thereof. Novel metal-organic framework.

7. In Paragraph 1, The above organic ligands are 1,3,5-benzenetricarboxylic acid, 4,4'-biphenyldicarboxilic acid, benzene-1,4-dicarboxylic acid, 9,10-anthracenedicarboxylic acid, biphenyl-3,3,5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 5-bromoisophthalic acid, and 5-cyano-1,3-benzenedicarboxylic acid. 2,2-diamino4,4'-stilbenedicarboxylic acid, 2,5-diaminoterephthalic acid, 1,1,2,2-tetra(4-carboxylphenyl)ethylene, 2,5-dihydroxyterephthalic acid, 2,2-dinitro-4,4-stilbenedicarboxylic acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 2-hydroxyterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 4,4,4''-s-triazine-2,4,6-triyl-tribenzoic acid6-triyltribenzoic acid), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-triscarboxyphenylethynylbenzene, 2-methylimidazole and One or more selected from the group consisting of 2-aminoterephthalic acid, Novel metal-organic framework.

8. In Paragraph 1, The above metal-organic framework exhibits a sustained antioxidant effect as the organic ligand degrades over time. Novel metal-organic framework.

9. In Paragraph 1, The above metal-organic framework maintains its antioxidant capacity even after more than 200 hours. Novel metal-organic framework.

10. In Paragraph 1, The above metal-organic framework exhibits an antioxidant capacity of 0.1% to 30% when exposed to light for 24 hours. Novel metal-organic framework having antioxidant activity.

11. A novel metal-organic framework according to any one of claims 1 to 10 Cosmetic composition.

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