CN116327640A - Bioadhesive hydrotalcite-polydopamine skin composite light shielding agent and preparation method thereof - Google Patents
Bioadhesive hydrotalcite-polydopamine skin composite light shielding agent and preparation method thereof Download PDFInfo
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- hydrotalcite
- light shielding
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- buffer solution
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- 229920001690 polydopamine Polymers 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 239000000227 bioadhesive Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 29
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 29
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 29
- 239000007853 buffer solution Substances 0.000 claims abstract description 28
- -1 zinc titanium cerium Chemical compound 0.000 claims abstract description 26
- 229960003638 dopamine Drugs 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 6
- 230000037072 sun protection Effects 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- YNIRKEZIDLCCMC-UHFFFAOYSA-K trisodium;phosphate;hydrate Chemical compound [OH-].[Na+].[Na+].[Na+].OP([O-])([O-])=O YNIRKEZIDLCCMC-UHFFFAOYSA-K 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 239000002114 nanocomposite Substances 0.000 abstract description 18
- 150000003254 radicals Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 8
- 239000000516 sunscreening agent Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002225 anti-radical effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 2
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- 206010008570 Chloasma Diseases 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 208000003351 Melanosis Diseases 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000035587 bioadhesion Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
- A61K2800/522—Antioxidants; Radical scavengers
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Gerontology & Geriatric Medicine (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a bioadhesive hydrotalcite-polydopamine skin compound light shielding agent and a preparation method thereof, wherein zinc titanium cerium hydrotalcite, dopamine and an oxidant in different proportions are added into a weak alkaline buffer solution under a light shielding condition to react for 3-72 hours at room temperature, the mixture is subjected to aftertreatment, and vacuum drying is carried out to obtain the bioadhesive hydrotalcite-polydopamine compound light shielding agent. The zinc-titanium-cerium hydrotalcite comprises the following components in percentage by weight: dopamine = 100:1-1:1; oxidizing agent: dopamine=50:1-1:1, reacting for 3-72h at 10-40 ℃; centrifuging the product at a rotating speed of 5000-11000 r/min for 1-15 min, washing for 3-8 times, and vacuum drying at 40-70 ℃ for 8-72h to obtain the ZnTiCe-LDH@PDA nanocomposite. The ZnTiCe-LDH@PDA nanocomposite material prepared by the preparation method provided by the invention has good light shielding property, light stability, free radical resistance, skin adhesion and water resistance.
Description
Technical Field
The invention relates to a light shielding agent, in particular to a hydrotalcite-polydopamine composite ultra-broad spectrum light shielding agent and a preparation method thereof, belonging to the field of functional composite materials.
Background
It is well known that prolonged excessive ultraviolet radiation is the cause of phototoxicity to the skin, photoaging of the skin and even cancer of the skin. With the knowledge of skin photodamage caused by sunlight, visible light has been found to have an effect on the skin. It can cause skin pigmentation, erythema, aggravate chloasma, etc. or cause solar urticaria, etc. Therefore, the protection of our life safety and health from sunlight using sun protection products is critical. However, the existing sun protection products are not ideal, because the sun protection agents have the problems of poor water resistance, insufficient protection breadth, active oxygen generation when exposed to strong sunlight, damage to skin and easy absorption by skin, potential safety hazard and the like.
In order to solve the defects of the sun-screening agent, the main solution thought proposed by the related researches (Journal of cosmetic dermatology,2019,18 (1): 315-321;Nature Materials,2015,14 (12): 1278-85;CN 113061256 A;CN112225894B) is to encapsulate the sun-screening agent into a nano-material so as to improve the sun-screening performance and the water-proof performance of the sun-screening agent and avoid the direct contact of the sun-screening agent and the skin, thereby avoiding the burden on the skin. Although the results of the related studies indicate that this method can effectively improve the above problems, there are also problems in that the ultraviolet protection area is limited and the protection against visible light is not provided. Therefore, the combination of the nano material package and the material with wide ultraviolet protection range and visible light blocking is one of the methods for breaking the bottleneck of the current light shielding material.
Hydrotalcite is a supermolecular compound composed of interlayer anions with negative charges and main laminates with positive charges, has low cost, good biocompatibility, ultraviolet resistance and excellent metal ion and anion exchange capacity, and has wide application in the fields of flame retardance, medicine, catalysis, sun protection and the like. The inorganic sun-screening agents zinc oxide and titanium dioxide have excellent ultraviolet blocking performance and are widely used in the sun-screening field; the zinc-titanium hydrotalcite can achieve the effect of combining the zinc-titanium hydrotalcite and has excellent ultraviolet shielding capability. Cerium-containing materials also exhibit good ultraviolet absorption in the study of other inorganic materials as sunscreens. Akemi Yasukawa et al reported for the first time that hydroxyapatite containing titanium and cerium, and found by study that hydroxyapatite containing titanium and cerium had better ultraviolet absorption properties in the UVA band than titanium alone (Colloids and Surfaces A,2021, 609:125705). Polydopamine is a bionic material of mussel protein, and has the properties of visible light absorption capacity, bioadhesion, good biocompatibility and eumelanin-like performance, namely, the damage of ultraviolet rays is resisted by scavenging free radicals. Tang Zuwu et al prepared a polydopamine-containing hydrogel, which was found to adhere to skin and to have good UV shielding, water repellency and biocompatibility after polydopamine modification (Cellulose, 2021, 28:1527-1540). The zinc-titanium-cerium hydrotalcite is modified by polydopamine, so that the light shielding agent with more excellent performance can be prepared by utilizing the respective advantages.
Disclosure of Invention
In order to solve the problems of poor waterproof capability, single protection range, potential safety hazard and the like of the existing sun-screening agent, the invention provides a novel bioadhesive hydrotalcite-polydopamine composite light shielding agent (ZnTiCe-LDH@PDA) and a preparation method of the light shielding agent. According to the invention, the surface of zinc-titanium-cerium hydrotalcite is modified by a one-pot method by utilizing the characteristic that dopamine is easily oxidized and self-polymerized by an oxidant in an alkaline environment, so that a polydopamine coating is formed on the surface of the zinc-titanium-cerium hydrotalcite, and the ZnTiCe-LDH@PDA nanocomposite is obtained. The material has good light shielding performance, shows strong absorption to UVB, UVA and visible light regions, does not generate active oxygen under ultraviolet irradiation, has good light stability, can resist free radicals, and plays a certain role in protecting skin. Furthermore, it is not washed away by water after a short incubation time of the skin, indicating that it has skin adhesion and is waterproof to the forces of the skin.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a bioadhesive hydrotalcite-polydopamine composite light shielding agent comprises the steps of adding zinc titanium cerium hydrotalcite, dopamine and an oxidant in different proportions into a weak alkaline buffer solution under a light-shielding condition, reacting for 3-72 hours at room temperature, carrying out post-treatment, and carrying out vacuum drying to obtain the bioadhesive hydrotalcite-polydopamine composite light shielding agent.
The invention provides a preparation method of the bioadhesive hydrotalcite-polydopamine composite light shielding agent, which comprises the steps of adding zinc-titanium-cerium hydrotalcite, dopamine and an oxidant in different proportions into a weak alkaline buffer solution under a light-shielding condition, reacting for 3-72 hours at room temperature, carrying out post-treatment, and carrying out vacuum drying to obtain the bioadhesive hydrotalcite-polydopamine composite light shielding agent.
Further, in the technical scheme, the zinc-titanium-cerium hydrotalcite comprises the following components in percentage by weight: dopamine = 100:1-1:1; oxidizing agent: dopamine=50:1-1:1, reacting for 3-72h at 10-40 ℃; centrifuging the product at a rotating speed of 5000-11000 r/min for 1-15 min, washing for 3-8 times, and vacuum drying at 40-70 ℃ for 8-72h to obtain the ZnTiCe-LDH@PDA nanocomposite. The ZnTiCe-LDH@PDA nanocomposite material prepared by the preparation method provided by the invention has good light shielding property, light stability, free radical resistance, skin adhesion and water resistance.
Further, in the above technical scheme, the chemical formula of the zinc-titanium-cerium hydrotalcite is [ Zn 2+ 1-x-y Ti 4+ x Ce 3+ y (OH) 2 ] (y+2x)+ (CO 3 2- ) (y+2x)/2 ·mH 2 O, wherein x is Ti 4+ /(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances; y is Ce 3+ /(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances; (Ti) 4+ +Ce 3+ )/(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances is x+y, and x+y is more than or equal to 0.12 and less than or equal to 0.65; ti (Ti) 4+ /Ce 3+ The mass ratio of the substances is x/y, and x/y is more than or equal to 1 and less than or equal to 20; m is the number of crystal water molecules, and m is more than or equal to 0.5 and less than or equal to 2.
Further, in the above technical scheme, the oxidizing agent is one or a combination of two or more of sodium periodate, ammonium persulfate, copper sulfate, hydrogen peroxide, potassium permanganate and potassium dichromate.
Further, in the above technical scheme, the buffer solution is one of N-tris (hydroxymethyl) methylglycine buffer solution, triethanolamine buffer solution, tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, disodium hydrogen phosphate-citric acid buffer solution, borax-sodium hydroxide buffer solution, and disodium hydrogen phosphate-sodium hydroxide buffer solution, and the pH is 7.5-12.0.
Further, in the technical scheme, the dosage ratio of the zinc-titanium-cerium hydrotalcite to the buffer solution is 0.5-5 g/100 mL.
The ZnTiCe-LDH@PDA nanocomposite is characterized by wide absorption range, can absorb light in UVB, UVA and visible light regions, can well provide protection against sunlight, and has excellent properties of light stability, free radical resistance, skin adhesion, water resistance and the like.
The zinc-titanium-cerium hydrotalcite has three elements of zinc, titanium and cerium, and can absorb ultraviolet rays in UVB and UVA areas. Polydopamine has light absorption capacity, free radical resistance, skin adhesion and water resistance due to its benzene ring, catechol and quinone structure.
The light shielding performance evaluation, the light stability evaluation, the free radical resistance evaluation and the skin adhesion and waterproof performance evaluation experiments of the ZnTiCe-LDH@PDA nanocomposite show that the material has the characteristics of excellent light shielding capability and skin friendliness.
Compared with the traditional sun-screening material, the invention is characterized in that:
(1) The zinc-titanium-cerium hydrotalcite has wide absorption range and good absorption capacity for ultraviolet rays in UVB and UVA regions.
(2) Compared with the traditional preparation method for the surface of the polydopamine modified material, the preparation method provided by the invention has the advantages of simplicity, high efficiency, low cost and the like by initiating dopamine autopolymerization through the oxidant.
(3) After the zinc-titanium-cerium hydrotalcite is modified by polydopamine, the light shielding property, the capability of resisting free radicals, the skin adhesiveness and the water resistance are obviously improved.
Drawings
In FIG. 1, (a) is a transmission electron microscope image of samples PL0 to 4, and (b) in FIG. 1 is an XRD image of samples PL0 to 4;
FIG. 2 is a graph of solid ultraviolet-visible diffuse reflectance spectra for samples PL 0-4;
FIG. 3 shows the photostability of samples PL 0-4; the left-to-right sequence in the histogram is the sequence of icons from left to right;
FIG. 4 shows the anti-radical ability of samples PL 0-4;
FIG. 5 shows skin adhesion and water repellency for Z samples PL 0-4;
wherein PL0 to 4 in the figure respectively represent zinc titanium cerium hydrotalcite prepared in comparative example and ZnTiCe-LDH@PDA nanocomposite materials generated in examples 1 to 4.
Detailed description of the preferred embodiments
The process of the present invention is further illustrated, but not limited, by the following examples.
(1) Preparation example of ZnTiCe-LDH@PDA nanocomposite
Comparative example
0.32g ZnCl is weighed out 2 、0.17g TiCl 4 、0.042g CeCl 3 .7H 2 O and 1.08g of urea were dissolved in a 50mL beaker, sonicated until the solution was clear, transferred to a hydrothermal kettle and crystallized at 150℃for 48h. And (3) cooling the hydrothermal kettle to room temperature, taking out slurry in the kettle, centrifuging, washing for several times, and putting the slurry into a vacuum drying oven for drying to obtain the zinc-titanium-cerium hydrotalcite PL0. From the transmission electron microscope pattern of PL0 in fig. 1 (a) and the XRD pattern of PL0 in fig. 1 (b), zinc-titanium-cerium hydrotalcite was produced.
Example 1
To 200mL of an N-tris (hydroxymethyl) methylglycine buffer solution or a triethanolamine buffer solution having ph=8, 4.00g of the zinc-titanium-cerium hydrotalcite ([ Zn) prepared in the comparative example was added 2+ 0.700 Ti 4+ 0.267 Ce 3+ 0.033 (OH) 2 ] 0.567+ (CO 3 2- ) 0.284 ·H 2 O), 0.08g of dopamine and 0.16g of ammonium persulfate, carrying out ultrasonic treatment for 30min, and reacting for 5h at room temperature; centrifuging the product at 6000r/min for 3min, washing for 3 times, and vacuum drying at 40 ℃ for 10h to obtain the ZnTiCe-LDH@PDA nanocomposite. As can be seen from the transmission electron microscope pattern of PL1 in FIG. 1 (a) and the XRD pattern of PL1 in FIG. 1 (b), znTiCe-LDH@PDA nanocomposite material was produced.
Example 2
To 200mL of tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution or disodium hydrogen phosphate-citric acid buffer solution having ph=9, 4.00g of zinc-titanium-cerium hydrotalcite ([ Zn) prepared in comparative example was added 2+ 0.700 Ti 4+ 0.267 Ce 3+ 0.033 (OH) 2 ] 0.567+ (CO 3 2- ) 0.284 ·H 2 O), 0.20g of dopamine and 0.40g of sodium periodate, carrying out ultrasonic treatment for 30min, and reacting for 10h at room temperature; centrifuging the product at 7000r/min for 6min, washing for 4 times, and vacuum drying at 50 ℃ for 15h to obtain the ZnTiCe-LDH@PDA nanocomposite. As can be seen from the transmission electron microscope pattern of PL2 in FIG. 1 (a) and the XRD pattern of PL2 in FIG. 1 (b), znTiCe-LDH@PDA nanocomposite material was produced.
Example 3
To 200mL of an N-tris (hydroxymethyl) methylglycine buffer solution having ph=10 or a borax-sodium hydroxide buffer solution, 4.00g of the zinc-titanium-cerium hydrotalcite ([ Zn) prepared in the comparative example was added 2+ 0.700 Ti 4+ 0.267 Ce 3+ 0.033 (OH) 2 ] 0.567+ (CO 3 2- ) 0.284 ·H 2 O), 0.40g of dopamine and 0.80g of copper sulfate, carrying out ultrasonic treatment for 30min, and reacting for 15h at room temperature; centrifuging the product at 6000r/min for 9min, washing for 5 times, and vacuum drying at 60 ℃ for 20h to obtain the ZnTiCe-LDH@PDA nanocomposite. As can be seen from the transmission electron microscope pattern of PL3 in FIG. 1 (a) and the XRD pattern of PL3 in FIG. 1 (b), znTiCe-LDH@PDA nanocomposite material was produced.
Example 4
To 200mL of disodium hydrogen phosphate-citric acid buffer solution or disodium hydrogen phosphate-sodium hydroxide buffer solution with ph=12.0, 4.00g of nano hydroxyapatite, 0.80g of dopamine and 1.60g of copper sulfate are added, and the mixture is subjected to ultrasonic treatment for 30min and reaction at room temperature for 20h; centrifuging the product at 10000r/min for 12min, washing for 6 times, and vacuum drying at 70 ℃ for 24h to obtain ZnTiCe-LDH@PDA nanocomposite. As can be seen from the transmission electron microscope pattern of PL4 in FIG. 1 (a) and the XRD pattern of PL4 in FIG. 1 (b), znTiCe-LDH@PDA nanocomposite material was produced.
(2) Performance examples of ZnTiCe-LDH@PDA nanocomposite
Example 5 (light shielding Performance test)
The light shielding performance of the materials of the present invention was tested using an ultraviolet/visible/near infrared spectrophotometer: recording solid UV-visible diffuse reflectance spectra of a Lambda 1050+ spectrophotometer equipped with an integrating sphere attachment at room temperature, and subjecting the BaSO to 4 As background. The results are shown in FIG. 2, and indicate that ZnTiCe-LDH@PDA has lower reflectivity in the range of 280-780nm, namely, strong absorption in the range.
Example 6 (light stability Performance test)
Each sample was weighed at room temperature and added to 75mL of methylene blue solution (5 mg/L), respectively, and stirred in the dark for 30min to reach adsorption-desorption equilibrium. Then, photodegradation reactions were carried out under ultraviolet light having wavelengths of 365nm and 254nm, respectively, and 3mL of the suspension was taken out from each beaker at predetermined intervals. Finally, the residual methylene blue content of the solution was determined by UV-visible spectroscopy at the maximum methylene blue absorption (664 nm). The test results were compared with rutile titanium dioxide commonly used in the industry and believed to be photostable and zinc titanium cerium hydrotalcite without polydopamine modification (fig. 3). As can be seen from fig. 3, znTiCe-ldh@pda hardly degraded methylene blue, indicating that it has good photo-stability.
Example 7 (anti radical capability test)
2mg of the prepared material was added to 4mL of a solution of 1, 1-diphenyl-2-picrylhydrazine (DPPH), respectively, and then reacted at ambient temperature in the absence of light for 30min. Finally, absorbance of each sample was measured at DPPH absorption maximum (517 nm) using an ultraviolet-visible spectrometer. Antioxidant activity is expressed as a percentage of DPPH radical inhibition, and the formula is as follows:
wherein Abs 0 And Abs i The absorbance values of the negative control (100% free radical) and the sample tested are represented, respectively. Calculating to obtain ZnTiCe-LDH@PDAAs shown in FIG. 4, compared with zinc-titanium-cerium hydrotalcite without polydopamine coating, the oxidation resistance of ZnTiCe-LDH@PDA is obviously improved.
Example 8 (skin adhesion and Water repellency test)
Firstly, the hair of fresh pigskin is carefully removed, so that the skin is prevented from being damaged. The treated clean pigskin is then stored at-20deg.C and thawed with physiological saline prior to use. The thawed pigskin was cut into 1X 1cm squares, 2mg of each sample was then applied evenly to the pigskin, incubated at room temperature for 30min, and then evaluated for skin adhesion and water repellency by simple rinsing, washing and wiping in 3 removal modes. The results before and after removal are shown in FIG. 5, which shows that ZnTiCe-LDH@PDA has excellent skin adhesion and water resistance compared with zinc titanium cerium hydrotalcite not modified by polydopamine.
Claims (10)
1. A preparation method of a bioadhesive hydrotalcite-polydopamine composite light shielding agent is characterized by comprising the following steps: under the condition of avoiding light, zinc-titanium-cerium hydrotalcite, dopamine and oxidant in different proportions are added into weak alkaline buffer solution, the mixture is reacted for 3 to 72 hours at room temperature, the post-treatment is carried out, and the bioadhesive hydrotalcite-polydopamine composite light shielding agent is obtained through vacuum drying.
2. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the chemical formula of the zinc-titanium-cerium hydrotalcite is [ Zn ] 2+ 1-x-y Ti 4+ x Ce 3+ y (OH) 2 ] (y+2x)+ (CO 3 2- ) (y+2x)/2 ·mH 2 O, wherein x is Ti 4+ /(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances; y is Ce 3+ /(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances; (Ti) 4+ +Ce 3+ )/(Zn 2+ +Ti 4+ +Ce 3+ ) The mass ratio of the substances is x+y, and x+y is more than or equal to 0.12 and less than or equal to 0.65; ti (Ti) 4+ /Ce 3+ The mass ratio of the substances is x/y, and x/y is more than or equal to 1 and less than or equal to 20; m is the number of crystal water molecules, and m is more than or equal to 0.5 and less than or equal to 2.
3. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the oxidant is one or more than two of sodium periodate, ammonium persulfate, copper sulfate, hydrogen peroxide, potassium permanganate and potassium dichromate, and the mass ratio of the oxidant to the dopamine is 50:1-1:1.
4. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the weight ratio of the zinc-titanium-cerium hydrotalcite to the dopamine is 100:1-1:1.
5. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the buffer solution is N-tris (hydroxymethyl) methylglycine buffer solution, triethanolamine buffer solution, tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, disodium hydrogen phosphate-citric acid buffer solution, borax-sodium hydroxide buffer solution, disodium hydrogen phosphate-sodium hydroxide buffer solution, and pH is 7.5-12.0.
6. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the dosage ratio of the zinc-titanium-cerium hydrotalcite to the buffer solution is 0.5-5 g/100 mL.
7. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the post-treatment is centrifugation and washing for 3-8 times.
8. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 7, wherein the method comprises the following steps: during centrifugal separation, the rotation speed is 5000-11000 r/min, and the centrifugal time is 1-15 min.
9. The method for preparing the bioadhesive hydrotalcite-polydopamine composite light shielding agent according to claim 1, wherein the method comprises the following steps: the temperature of vacuum drying is 40-70 ℃ and the time is 8-72h.
10. The bioadhesive hydrotalcite-polydopamine composite light shielding agent obtained by the preparation method according to any one of claims 1 to 9 is applied to the field of sun protection.
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