CN109276474B - Preparation method of nano zinc oxide/cationic polysaccharide hybrid nano particles - Google Patents
Preparation method of nano zinc oxide/cationic polysaccharide hybrid nano particles Download PDFInfo
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- CN109276474B CN109276474B CN201811157702.5A CN201811157702A CN109276474B CN 109276474 B CN109276474 B CN 109276474B CN 201811157702 A CN201811157702 A CN 201811157702A CN 109276474 B CN109276474 B CN 109276474B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 44
- -1 cationic polysaccharide Chemical class 0.000 title claims abstract description 33
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 30
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 12
- 230000000475 sunscreen effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 41
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 33
- 229920001661 Chitosan Polymers 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000004201 L-cysteine Substances 0.000 claims description 12
- 235000013878 L-cysteine Nutrition 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 230000010494 opalescence Effects 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000011358 absorbing material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 37
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 150000001413 amino acids Chemical class 0.000 abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 10
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000002835 absorbance Methods 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 229940079877 pyrogallol Drugs 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 description 2
- AMUTYVGRCVFCCD-UHFFFAOYSA-N 5,6-diaminopyridine-3-carboxylic acid Chemical compound NC1=CC(C(O)=O)=CN=C1N AMUTYVGRCVFCCD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 231100000245 skin permeability Toxicity 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229940032094 squalane Drugs 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- 101800000068 Antioxidant peptide Proteins 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JIRMQEPRKFTWOK-UHFFFAOYSA-L O.O.O.O.O.O.[Zn+2].CC([O-])=O.CC([O-])=O Chemical compound O.O.O.O.O.O.[Zn+2].CC([O-])=O.CC([O-])=O JIRMQEPRKFTWOK-UHFFFAOYSA-L 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/025—Explicitly spheroidal or spherical shape
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/447—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof containing sulfur
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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
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
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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
- A61K8/73—Polysaccharides
- A61K8/735—Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
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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
- A61K8/73—Polysaccharides
- A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
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- 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
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Abstract
The invention discloses a nano zinc oxide/cationic polysaccharide hybrid nano particle and a preparation method thereof, belonging to the technical field of composite nano particles. The nanometer zinc oxide/cationic polysaccharide hybrid nano-particles are prepared from the cationic polysaccharide/sulfhydryl-containing amino acid/nanometer zinc oxide precursor mixed solution, the preparation method is simple, and the cost is low. Compared with the existing particle material, the hybrid nano-particle has better dispersibility, light stability, lower photocatalytic activity, better oxidation resistance and emulsifying property, and can be used in sunscreen skin care products and other anti-ultraviolet materials.
Description
Technical Field
The invention relates to a nano zinc oxide/cationic polysaccharide hybrid nano particle and a preparation method thereof, belonging to the field of composite nano particles.
Background
An inorganic sunscreen agent is a physical sunscreen agent that functions as a sun screen by reflecting, refracting, and scattering ultraviolet rays, and is called an inorganic nano sunscreen agent when its particle size is 1 to 100 nm. Compared with common inorganic sun-screening agents, the inorganic nano sun-screening agent has small particle size and large specific surface area, can absorb ultraviolet rays and reflect the ultraviolet rays, and has stronger blocking capability on the ultraviolet rays. However, the particle size is small, the specific surface area is large, so that the photocatalyst is easy to agglomerate, has high photocatalytic activity, is easy to permeate into skin, and causes potential harm to the health of people. In order to solve the problems of easy agglomeration, high photocatalytic activity, easy skin penetration and the like, at present, a surface covering and coating method is mainly adopted, for example, titanium dioxide particles are coated by using alumina, fatty acid, dimethyl polysiloxane, natural macromolecules and the like, so that the titanium dioxide particles have the following characteristics: the surface is inertized, and the photochemical stability is improved; secondly, the particle size is increased after coating, and the skin permeability is reduced; the surface of the titanium dioxide is provided with different functional groups, and the titanium dioxide subjected to surface treatment can be well dispersed in different media.
For example, Xiaojie et al [ Xiao J, Chen W, Wang F, et al, Polymer/TiO2 nanoparticles with high Effective UV-Screening but electrically amplified photocatalytic Activity [ J].Macromolecules,2013,46(2):375-383.]The triblock polymer PEO-b-PDMA-b-PS is self-assembled in THF/EtOH to prepare colloidal particles with a core-shell structure, then the precursor tetraethyl titanate of nano titanium dioxide is added into a micellar solution, and the polymer/TiO2hybrid colloidal particles are prepared through a sol-gel reaction, so that the nano titanium dioxide hybrid colloidal particles have good dispersibility, low photocatalytic activity and good sun-screening performance. Recently, Anna Regiel et al [ Regielfutyra A,
M,
S,et al.The quenching effect of chitosancrosslinking on ZnO nanoparticles photocatalytic activity[J].Rsc Advances,2015,5(97):80089-80097.]it is reported that chitosan is crosslinked on the surface of nano zinc oxide by blending chitosan and nano zinc oxide and adding a crosslinking agent sodium tripolyphosphate so as to improve the dispersibility of the nano zinc oxide and quench the photochemical activity of the nano zinc oxide.
However, the particle diameter of the particles obtained by the current method is relatively large, the dispersibility is poor, and the photocatalytic activity is not obviously inhibited, so that the development of the nano sunscreen agent is restricted.
Disclosure of Invention
In order to solve the problems of poor dispersibility, high photocatalytic activity and easy penetration into skin of nano zinc oxide in the prior art, the invention researches a nano zinc oxide modification method, prepares nano zinc oxide/cationic polysaccharide hybrid nano particles through a cationic polysaccharide/L-cysteine/nano zinc oxide precursor mixed solution, and obtains the nano zinc oxide/cationic polysaccharide hybrid nano particles which have good dispersibility, low photocatalytic activity and low skin permeability and are hybrid nano sunscreen particles with sunscreen and antioxidant functions.
The first object of the invention is to provide a preparation method of nano zinc oxide/cationic polysaccharide hybrid nano particles, which comprises the following steps:
(1) mixing the cationic polysaccharide solution and the mercapto-containing amino acid solution, adding a nano zinc oxide precursor, and stirring at room temperature for 24 hours until the nano zinc oxide precursor is completely dissolved to obtain a mixed solution of cationic polysaccharide/L-cysteine/nano zinc oxide precursor;
(2) and adding an alkaline water solution into the mixed solution to adjust the pH of the mixed solution to 7, wherein the solution presents blue opalescence, and thus the hybrid nano-particles are obtained.
In one embodiment of the present invention, the mass concentration ratio of the cationic polysaccharide to the mercapto-containing amino acid is (0.5 to 6): 1.
In one embodiment of the invention, the mass concentration ratio of the nano zinc oxide precursor to the mercapto-containing amino acid is (0.1-6): 1.
In one embodiment of the present invention, the preparation method of the nano zinc oxide/cationic polysaccharide hybrid nano particles specifically comprises the following steps: preparing a cationic polysaccharide aqueous solution, preparing a sulfhydryl-containing amino acid aqueous solution, mixing the two aqueous solutions in equal volumes, adding a nano zinc oxide precursor, stirring at room temperature for 24 hours until the nano zinc oxide precursor is completely dissolved, adjusting the pH of the mixed solution to 5-8 by using an alkaline regulator, and enabling a colorless solution to show blue opalescence to obtain nano zinc oxide/cationic polysaccharide hybrid nanoparticles;
the dosage of each reactant is calculated according to the following formula by weight fraction:
10-200 parts of cationic polysaccharide,
20-100 parts of amino acid containing sulfhydryl groups,
50-200 parts of a nano zinc oxide precursor.
In an embodiment of the invention, the precursor of the nano zinc oxide in the mixed solution is one or a mixture of more of anhydrous zinc acetate, zinc acetate dihydrate, zinc acetate hexahydrate and zinc carbonate.
In one embodiment of the invention, the concentration of the nano zinc oxide precursor is 0.5-10 mg/mL.
In one embodiment of the invention, zinc acetate is preferably selected as the nano zinc oxide precursor, and the concentration of the zinc acetate is 5-10 mg/mL.
In one embodiment of the invention, the thiol-group-containing amino acid comprises L-cysteine or an amino acid that is chemically modified with a thiol group.
In one embodiment of the invention, the cationic polysaccharide comprises a mixture of one or more of quaternized chitosan, cationized hyaluronic acid, cationic guar gum, cationic cellulose.
In one embodiment of the invention, the cationic polysaccharide solution is 1-6 mg/mL aqueous solution.
In one embodiment of the invention, the mercapto amino acid-containing solution is 2-4 mg/mL aqueous solution.
In one embodiment of the present invention, the volume ratio of the cationic polysaccharide solution to the mercapto amino acid-containing solution is 1: (1-1.5).
In one embodiment of the present invention, the alkaline regulator is preferably aqueous NaOH solution with a concentration of 0.4-0.6M.
The second purpose of the invention is to provide the nano zinc oxide/cationic polysaccharide hybrid nano particles prepared by the method.
It is a third object of the present invention to provide a cosmetic preparation comprising the nano zinc oxide/cationic polysaccharide hybrid nano-particles according to claim 8.
In one embodiment of the invention, the cosmetic preparation comprises a cosmetic oil or lotion or cream.
The fourth purpose of the invention is to provide the application of the nano zinc oxide/cationic polysaccharide hybrid nano particles in the field of cosmetic sunscreen or other ultraviolet-resistant absorbing materials.
The invention has the beneficial effects
The raw materials of the cationic polysaccharide and the sulfhydryl-containing amino acid for preparing the hybrid nano-particles are cheap and easy to obtain, have good biocompatibility, and are simple and convenient in preparation process, and the cationic polysaccharide has a free radical scavenging function, so that the hybrid nano-particles are endowed with oxidation resistance, and can be well used for whitening skin care products. The invention solves the problems of easy agglomeration and poor dispersibility of the nano zinc oxide due to the particle size, and the cationic polysaccharide and the amino acid containing sulfhydryl group wrap the nano zinc oxide in the self-assembly process, thereby also solving the problems of easy permeation, poor light stability and photocatalytic activity and effectively shielding ultraviolet radiation. The hybrid particles prepared by the invention have better emulsifying performance to different cosmetic oils, and can be used as an emulsifier in the preparation of emulsion cream and the like.
Drawings
FIG. 1 is an infrared spectrum of a hybrid colloidal particle prepared according to the present invention;
FIG. 2 is TEM and SEM images of the hybrid colloidal particles prepared by the present invention, wherein (A1), (B1) are TEM and SEM images of example 1, respectively, (A2), (B2) are TEM and SEM images of example 2, respectively, (A3), (B3) are TEM and SEM images of example 3, respectively;
FIG. 3 is a graph of UV transmittance of hybrid colloidal particles prepared according to the present invention;
FIG. 4 is a graph showing the degradation rate of the hybrid colloidal particles prepared according to the present invention to rhodamine;
FIG. 5 is a graph of the rate of removal of DPPH radicals by hybrid colloidal particles prepared in accordance with the present invention;
FIG. 6 is a graph showing the emulsification effect of the hybrid colloidal particles prepared according to the present invention on various cosmetic oils.
Detailed Description
Testing the photodegradation rate of rhodamine B:
the specific experimental operation method comprises the following steps: adding rhodamine B into ZnO, QAC/L-Cys/ZnO-5, QAC/L-Cys/ZnO-7.5 and QAC/L-Cys/ZnO-10 colloidal particle solutions to enable the concentration of the rhodamine B to be 0.1mg/mL, irradiating the colloidal particle solutions for different times by using an ultraviolet lamp, sampling 10mL of sample liquid, carrying out centrifugal separation at 10000r/min, measuring the absorbance A of supernatant liquid at 554nm, determining the concentration of rhodamine B dye in the solution, and calculating the degradation rate of the rhodamine B according to the formula (1).
Percent degradation rate (%) [ (A)0-A)/A0]×100％ (1)
In the formula A0And A is the absorbance of the rhodamine B solution before and after the light treatment respectively.
Free radicals (DPPH, OH, O)2) Cleaning efficiency map test of (1):
DPPH clearance assay: 1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH) is a synthetic free radical with a single electron and centered on nitrogen, can exist in an alcohol solution very stably and presents purple color, and has a strong absorption peak at 517 nm. When DPPH and the antioxidant exist simultaneously, DPPH can absorb electrons or hydrogen atoms carried by the antioxidant and can be paired with lone pair electrons carried by DPPH to form a more stable colorless compound, and the amount of free radicals can be accurately and quickly detected by a spectrophotometer through color change. DPPH clearance rate is widely used for evaluating the ability of antioxidant substances to scavenge free radicals due to its advantages of convenience, rapidness, stability and the like.
Referring to the periwinkle method, 0.5mL of sample solution was added to 8X 10 solutions-5mol L-1The DPPH absolute ethyl alcohol solution is 2.5mL, the mixture is uniformly mixed, the mixture is subjected to shading reaction for 45min at room temperature, the mixture is centrifuged for 10min at 4000r/min, the absorbance value is measured at 517nm, each sample is measured for three times in parallel, and DPPH clearance is calculated according to formula 2.
In the formula: a. the0-control (0.5mL water +2.5mL DPPH solution) absorbance value; a. thei-absorbance values of sample sets (0.5mL sample solution +2.5mL DPPH solution); a. thej-absorbance values for blanks (0.5mL sample solution +2.5mL absolute ethanol solution).
Determination of OH clearance: hydroxyl radical scavenging experiment by scavenging Fe2+/H2O2OH in the system is used for determining the capability of the antioxidant peptide for eliminating hydroxyl radicals. With a slight modification of the method referred to Wuyue, 2mL of 9mmol L were added in sequence-1FeSO of (2)4Solution, 2mL 9mmol L-1Salicylic acid (II)Ethanol solution, 2mL antioxidative peptide solution in 10mL test tube, and finally 2mL8.8mmol L-1H of (A) to (B)2O2The solution was shaken in a 37 ℃ water bath for 1 h. While deionized water was used as a blank. The absorbance values of the solutions were determined in parallel 3 times at 536 nm. The hydroxyl radical clearance was calculated using the following formula 3:
in the formula: a. theoThe absorbance of the blank control solution; a. thesAbsorbance of the added sample.
O2And (3) determination of clearance rate: the superoxide anion radical clearance rate is determined by adopting a pyrogallol method in the experiment. With a slight modification to the peri-xuhui method, 0.3mL of the sample solution and 5mL of Tris-HCl (pH 8.2) buffer solution were added to a 10mL stoppered tube and the tube was then incubated at 37 ℃ for 20 min. 0.3mL of 7.5mmol L was added to a stoppered tube-1The pyrogallol solution is evenly oscillated, the absorbance value of the pyrogallol solution is rapidly measured once every 5 seconds at 320nm, and the reaction is carried out for 80 seconds. Plotting the absorbance against time, wherein the slope is the pyrogallol autoxidation rate A of the sample solutions. The sample is replaced by 0.3mL of Tris-HCl buffer solution, and the pyrogallol autoxidation rate A is measured by the methodoIn parallel three times. Superoxide anion radical clearance was calculated according to equation 4:
in the formula: a. theoThe absorbance of the blank control solution; a. thesIs the absorbance after addition of the sample.
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited thereto.
Example 1:
the preparation method of the nano zinc oxide/quaternized chitosan hybrid nano particles comprises the step of preparing the nano zinc oxide/quaternized chitosan hybrid nano particles with the concentration of 3mg mL-120mL, 3mg mL of a 0.5 wt% aqueous quaternized chitosan (QAC)-120mL of L-cysteine aqueous solution, and mixing the two solutions in equal volumeAdding nano zinc oxide precursor to make its concentration be 2mg mL-1And stirring for 24 hours at room temperature to uniformly mix the components, finally adjusting the pH of the solution to 7 by using 0.5M NaOH, and enabling the colorless solution to show blue opalescence, namely the required nano zinc oxide/quaternized chitosan hybrid nano particles (QAC/L-Cys/ZnO-2).
Example 2:
the preparation method of the nano zinc oxide/quaternized chitosan hybrid nano particles comprises the step of preparing the nano zinc oxide/quaternized chitosan hybrid nano particles with the concentration of 3mg mL-120mL, 3mg mL of the 0.5 wt% QAC aqueous solution-120mL of L-cysteine aqueous solution, mixing the two solutions in equal volume, and adding a nano zinc oxide precursor to make the concentration of the precursor be 4mg mL-1And stirring for 24 hours at room temperature to uniformly mix the components, finally adjusting the pH of the solution to 7 by using 0.5M NaOH, and enabling the colorless solution to show blue opalescence, namely the required nano zinc oxide/quaternized chitosan hybrid nano particles (QAC/L-Cys/ZnO-4).
Example 3:
the preparation method of the nano zinc oxide/quaternized chitosan hybrid nano particles comprises the step of preparing the nano zinc oxide/quaternized chitosan hybrid nano particles with the concentration of 3mg mL-120mL, 3mg mL of the 0.5 wt% QAC aqueous solution-120mL of L-cysteine aqueous solution, mixing the two solutions in equal volume, and adding a nano zinc oxide precursor to make the concentration of the precursor be 6mg mL-1And stirring for 24 hours at room temperature to uniformly mix the components, finally adjusting the pH of the solution to 7 by using 0.5M NaOH, and enabling the colorless solution to show blue opalescence, namely the required nano zinc oxide/quaternized chitosan hybrid nano particles (QAC/L-Cys/ZnO-6).
Comparative example 1:
the preparation concentration is 1mg mL-1Adding 60mg of nano zinc oxide into 60mL of chitosan aqueous solution, adding 120mg of cross-linking agent sodium tripolyphosphate (TPP, QAC: ZnO: TPP ═ 1:1:2), magnetically stirring for 15min, then carrying out ultrasonic treatment for 30min, then centrifuging the sample (4000rpm, 5 min), washing and precipitating twice with distilled water to obtain CS @ zinc oxide; they were resuspended directly in water before further testing.
Example 4 the hybrid nanoparticles obtained above were subjected to performance tests:
total inversion of QAC, ZnO, L-cysteine and QAC/L-Cys/ZnO hybrid colloidal particlesAnd (3) testing the radio infrared spectrum: electrostatic interaction between protonated amino and hydroxyl in QAC and anionic carboxyl in L-cysteine and complexation between L-cysteine and ZnO can induce formation of QAC/L-Cys/ZnO hybrid colloidal particles. FTIR spectra of pure QAC, L-cysteine, ZnO and hybrid colloidal particles indicated that hybrid formed during mixing, as shown by IR in FIG. 1, 1658cm in QAC spectrum-1Is the stretching vibration peak of amide I with carbonyl (C ═ O), and 1576cm-1Is a combination of the amide II band and the N-H bending vibration of the amino group in the deacetylation unit. 3182cm in an L-cysteine spectrogram-1Is hydroxy on carboxyl and-NH2Characteristic peak of (2), 2537cm-1Is a characteristic peak of-SH, and a characteristic peak of hydroxyl on ZnO is 3416cm-1. In QAC/ZnO spectrogram, the-SH characteristic peak disappears, and the interaction between sulfydryl and nano zinc oxide is proved, wherein 3300cm-1The characteristic peak became broad and strong due to the generation of hydrogen bonds, and 1037cm-1Is a characteristic peak of the glycosidic bond (C-O-C) on the QAC, and proves the successful preparation of QAC/L-Cys/ZnO hybrid colloidal particles.
The product performance of the obtained hybrid nanoparticles was performed as shown in table 1:
TABLE 1 hybrid nanoparticle product Properties
As can be seen from Table 1, the particle size of the nanoparticles obtained in the comparative example is 178nm, while the hybrid nanoparticles prepared from the hybrid colloidal particles obtained in examples 1, 2 and 3 are spherical (FIG. 2), the particle sizes are respectively about 100nm, 120nm and 150nm, the particle size can be reduced by 15.7%, preferably 43.8%, and the dispersion is more uniform;
as can be seen from fig. 3, the transmittances of the QAC and L-cysteine alone and the simple mixed solution thereof in the 230-420nm band are both about 80%, the transmittance is higher, whereas the ultraviolet absorption rate is lower, and the transmittance of the prepared hybrid nanoparticles is significantly reduced, and increases with the increase of the concentration of the nano zinc oxide, and the maximum transmittance of the invention in the band can be reduced to 10%, which indicates that the hybrid nanoparticles have better ultraviolet absorption performance;
the degradation rate of the nano zinc oxide to rhodamine B after 5h is 95% (figure 4), and as can be seen from table 1, the photocatalytic activity of the hybrid colloidal particles obtained in examples 1, 2 and 3 is obviously reduced to only 1.5%, 3% and 4.6%, while the photocatalytic activity of comparative example 1 is larger to 12.7%, which shows that the coating of nano zinc oxide with quaternized chitosan can effectively shield the photocatalytic activity of nano zinc oxide, and more-NH on quaternized chitosan2And active hydrogen on-OH can efficiently remove free radicals, thereby greatly reducing the photocatalytic activity of the photocatalyst;
furthermore, after 24h, the hybrid colloidal particles obtained from example 1 were paired with DPPH, OH, O2The maximum clearance rates of the three free radicals are 81.3%, 46.8% and 60.2% respectively; the hybrid colloidal particle pair DPPH, OH, O obtained from example 22The maximum clearance rates of the three free radicals are respectively 80.9%, 40.2% and 57.9%; the hybrid colloidal particle pair DPPH, OH, O obtained from example 32The maximum clearance rates of the three free radicals are respectively 78.1%, 36.9% and 52.6%; comparative example nanoparticles obtained for DPPH, OH, O2The maximum clearance rates of the three free radicals are respectively 79.7%, 26.0% and 37.3%, and the clearance efficiency is lower, which shows that the hybrid colloidal particles have better free radical clearance function and can prevent the skin from being damaged by the free radicals;
as can be seen from FIG. 6, the QAC/ZnO-6 hybrid colloidal particles obtained were able to stabilize not only white oil but also various cosmetic oils such as squalane, isooctyl palmitate, olive oil, etc., wherein the emulsion prepared with squalane, isooctyl palmitate, olive oil as the oil phase was able to be stably left for two months. The colloidal particles have certain universality and potential application value in the field of cosmetics.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are possible within the spirit and scope of the appended claims.
Claims (5)
1. A method for preparing nano zinc oxide/cationic polysaccharide hybrid nano particles for resisting ultraviolet rays, which is characterized by comprising the following steps:
the preparation concentration is 3mg mL-120mL, 3mg mL of the 0.5 wt% aqueous quaternized chitosan solution-120mL of L-cysteine aqueous solution, mixing the two solutions in equal volume, and adding a nano zinc oxide precursor to make the concentration of the precursor 2mg mL-1And stirring for 24 hours at room temperature to uniformly mix the nano zinc oxide/quaternized chitosan hybrid nano particles, and finally adjusting the pH of the solution to 7 by using 0.5M NaOH to obtain a colorless solution which presents blue opalescence, namely the required nano zinc oxide/quaternized chitosan hybrid nano particles.
2. The nano zinc oxide/cationic polysaccharide hybrid nano-particles prepared by the method of claim 1.
3. A cosmetic preparation comprising the nano zinc oxide/cationic polysaccharide hybrid nano-particle of claim 2.
4. A cosmetic preparation according to claim 3, comprising a cosmetic oil or an emulsion or cream.
5. The use of the nano zinc oxide/cationic polysaccharide hybrid nano particles as claimed in claim 2 in the field of cosmetic sunscreen or anti-ultraviolet absorbing materials.
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