CN116747154B - Cerium oxide-based sun-screening material capable of resisting blue light and preparation method thereof - Google Patents
Cerium oxide-based sun-screening material capable of resisting blue light and preparation method thereof Download PDFInfo
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 100
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000012216 screening Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 83
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 54
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 31
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 31
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 31
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 239000000516 sunscreening agent Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 230000000475 sunscreen effect Effects 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000037072 sun protection Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 241000192125 Firmicutes Species 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 201000004569 Blindness Diseases 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 230000032677 cell aging Effects 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 208000030533 eye disease Diseases 0.000 description 1
- 210000000887 face Anatomy 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011506 response to oxidative stress Effects 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 239000002884 skin cream Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- A61K8/41—Amines
-
- 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
- A61K8/67—Vitamins
- A61K8/676—Ascorbic acid, i.e. vitamin C
-
- 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
- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- 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
- A61K2800/524—Preservatives
-
- 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
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/614—By macromolecular compounds
Abstract
The invention discloses a cerium oxide-based sun-screening material capable of resisting blue light and a preparation method thereof, wherein the sun-screening material comprises the following components: polyethyleneimine, triethylamine, cerium nitrate hexahydrate, L-ascorbic acid and silver nitrate. The sun-screening material disclosed by the invention has excellent ultraviolet resistance, blue light resistance, bacteriostasis and good biocompatibility. The invention solves the problems of light pollution related to light aging and the like from ultraviolet light and short-wave blue light bands, and the synthesis method adopts simple chemical precipitation.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a cerium oxide-based sun-screening material capable of resisting blue light and a preparation method thereof.
Background
Short-wave blue light is a section of visible light wave in the blue light region and is located at 400-450 and nm. The device mainly derives from natural light and an electronic display screen, eye diseases with different degrees, such as vision degradation, cataract, blindness and the like, are generated by the radiation of the electronic display screen, and scientific researchers find that a large amount of high-energy short-wave blue light with irregular frequency is contained in light rays emitted by the screen in the test of the electronic screen, and the blue light wave has strong length and penetrability, can induce oxidative stress reaction and induce cell damage; the light also has an accumulation effect, and long-time contact or exposure to short-wave blue light can reduce the activity of cells and change the physiological form of normal cells. Therefore, the physiological damage caused by the short-wave blue light is not inferior to ultraviolet rays at all.
However, the blue light prevention technology in the cosmetic field is mainly used for relieving pigmentation, delaying skin aging and cell passage, and has little research on the development of physical radiation absorption; meanwhile, the existing physical sun-screening and chemical sun-screening agents can not filter and shield short-wave blue light, and the existing physical sun-screening materials such as titanium dioxide and zinc oxide are frequently used in cosmetic use scenes at present, so that skin is often bluish and white, and skin is easily dried and peeled; zinc oxide is similar to pseudo white and sticky, and because the two have strong photocatalytic activity, free radicals are easy to generate during use, and cell aging is accelerated.
In view of the above, novel composite materials are developed based on cerium oxide and the like, and are used for solving the problem of shortwave blue light hazard faced by people.
Disclosure of Invention
The invention aims to provide a cerium oxide-based sun-screening material capable of resisting blue light, shielding ultraviolet rays and inhibiting bacteria, and can be used as an ultraviolet and blue light shielding agent of an oxide-based composite material and a novel physical sun-screening agent.
The invention also aims at providing a preparation method of the cerium oxide-based sun-screening material capable of resisting blue light.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a ceria-based sun protection material that is resistant to blue light, comprising the following components: polyethyleneimine (PEI), triethylamine (TEA), cerium nitrate hexahydrate (Ce (NO) 3 ） 3 ·6H 2 O), L-ascorbic acid (L-AC), silver Nitrate (SN); the molar ratio of the polyethyleneimine PEI to the cerium nitrate hexahydrate (Ce (NO 3) 3.6H2O) is 2-4:1-10; the triethylamine TEA and cerium nitrate hexahydrate (CThe molar ratio of e (NO 3) 3.6H2O is 5-20:1-200; the molar ratio of the L-ascorbic acid (L-AC) to the cerium nitrate hexahydrate (Ce (NO 3) 3.6H2O) is 1-2:120-600; the molar ratio of the Silver Nitrate (SN) to the cerium nitrate hexahydrate (Ce (NO 3) 3.6H2O) is 1-2:100-250.
The invention provides alkaline environment to control pH by using Triethylamine (TEA), and further uses cerium nitrate hexahydrate (Ce (NO) 3 ） 3 ·6H 2 O) reaction, polyethyleneimine (PEI) as a template agent, with its adhesion to cerium oxide (CeO) 2 ) The surface is rich in amine groups, and the primary modified cerium oxide (CeO) with a certain blue light resisting performance is obtained 2 -PEI); taking silver Nitrate (NS) as a silver source and L-ascorbic acid (L-AC) as a reducing agent, and further carrying out reduction reaction on the silver Nitrate (NS) and modified cerium oxide (CeO) 2 PEI) surface amino complexing to prepare the cerium oxide-based sun-screening material capable of resisting blue light.
The preparation method of the cerium oxide-based sun-screening material capable of resisting blue light comprises the following steps:
s1, dissolving cerium nitrate hexahydrate in absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution A;
s2, dissolving polyethyleneimine in absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution B;
s3, slowly adding the solution B into the solution A until a large amount of white floccules appear, adding triethylamine, reacting for a certain time t1, adding pure water for hydrolysis reaction after water cooling, continuously cooling for a certain time t2, and then reacting for a certain time t3 at room temperature to obtain a suspension C;
s4, washing the suspension C to be neutral by pure water, further centrifugally washing by absolute ethyl alcohol and pure water, drying and grinding to obtain solid powder E;
s5, dispersing the solid powder E in pure water by ultrasonic, and dripping 2V/V% ammonia water to obtain turbid liquid F;
s6, adding the silver ammonia solution H into the turbid liquid F, carrying out light-shielding treatment, adding the L-ascorbic acid aqueous solution G under high-speed stirring after reacting for a certain time t4, and reacting for a certain time t5 at room temperature by changing the rotating speed to obtain turbid liquid I;
and S7, carrying out suction filtration on the turbid liquid I to obtain a gray brown precipitate, respectively washing with absolute ethyl alcohol and pure water, and drying to obtain gray brown powder, thus obtaining the cerium oxide-based sun-screening material capable of resisting blue light.
Preferably, the concentration of the solution A is 30W-50W/V, and the addition amount of the absolute ethyl alcohol is 15 mL.
Preferably, the concentration of the solution B is 2.5W/V-10W/V, and the addition amount of the absolute ethyl alcohol is 10mL.
Preferably, in the step S3, the weight of the triethylamine TEA is 5-15g.
Preferably, the reaction time t in the step S3 1 For 20-60 min, preferably 350ml pure water is added, and cooling is continued for a period t 2 1-15 min, reaction time t at room temperature 3 1-4 h.
Preferably, the concentration of the solid powder E in the step S5 is 1-10W/V%, preferably 10mL of pure water is added.
Preferably, the step S6 further includes: l-ascorbic acid is dissolved in pure water and stirred well to give an aqueous L-ascorbic acid solution G having a concentration of 2 to 5W/V%, preferably 0.4mL of pure water.
Preferably, the step S6 further includes: silver nitrate is dissolved in pure water and stirred fully, 2V/V% ammonia water is dripped into the mixture to obtain silver ammonia solution H, the concentration of the silver ammonia solution H is 0.1-0.5W/V%, and the addition amount of the pure water is preferably 5 mL.
Preferably, the reaction time t in the step S6 4 The high-speed stirring is carried out for 10-30 min at a rotating speed of 1000-2000 rad/min for 1-5 min, and the room temperature reaction time t is changed at a rotating speed of 400-600 rad/min 5 2-10 h.
Preferably, the drying conditions in the step S4 and the step S7 are drying for 1-3 hours at the temperature of 95-115 ℃.
The invention uses a certain amount of Polyethyleneimine (PEI) as a template agent for cerium oxide CeO 2 Surface modification is carried out, and the modified cerium oxide CeO 2 The PEI surface contains a plurality of amine groups, whichThe amino group can be effectively complexed with silver particles, in addition, N atoms in the functional group structure have strong electron donating ability, so that the lone pair electrons can be transferred to the surface of nano silver through the interaction of the N atoms after silver loading, thereby prolonging the service life of the composite material (Ag NPs@CeO) 2 -PEI).
The polyethyleneimine is a degradable molecular polymer with high adhesiveness and high adsorptivity, has good biocompatibility and cytotoxicity, and the loaded nano silver has good biocompatibility. Dendritic Polyethylenimine (PEI) is a highly adhesive, highly adsorptive polymer rich in primary, secondary and tertiary amine groups, a good biocompatible and water-soluble material.
The invention utilizes cerium oxide CeO 2 With unique 4F 1 The electronic structure makes its radiation have spectral selectivity, so cerium oxide can effectively shield visible to infrared band.
The invention takes L-ascorbic acid (L-AC) as a reducing agent to reduce silver Nitrate (NS) to prepare nano silver, and the nano silver is assembled and attached to the modified precursor cerium oxide (CeO) 2 -PEI) surface, such that finally prepared cerium oxide (Ag NPs@CeO) 2 -PEI) has the optical and antibacterial properties of nano silver.
The invention not only relates to cerium oxide CeO 2 The surface is modified, silver nitrate is used for doping, so that silver particles in the solution are uniformly loaded with precursor cerium oxide CeO in a chemical bond mode 2 The surface of PEI is reduced and regulated by L-ascorbic acid with a certain concentration, and the growth of silver particles on the surface of PEI is promoted, so that nano silver is uniformly and successfully loaded on the precursor cerium oxide CeO 2 The surface of PEI is endowed with optical property and antibacterial property, and the prepared cerium oxide-based sun-screening material capable of resisting blue light (Ag NPs@CeO) 2 -PEI）。
Compared with the prior art, the invention has the following beneficial effects:
1. the cerium oxide-based sun-screening material capable of resisting blue light adopts a simple and convenient chemical precipitation method, is simple, controllable and mild in operation, utilizes polyethyleneimine to construct the surface of cerium oxide, so that the surface of the cerium oxide is rich in various amino groups, can be effectively complexed with metal elements (such as gold, silver, copper, zinc and the like) in a chemical bond mode, has electron donating capacity and prolonged service life, can be used as an oxide-based composite material blue light, an ultraviolet screening agent and a novel physical sun-screening agent, and has excellent ultraviolet resistance, blue light resistance, bacteriostasis, good biocompatibility, excellent comprehensive performance, low cost and wide application field.
2. The cerium oxide-based sun-proof material capable of resisting blue light provided by the invention has the advantages that nano silver is selected as a doped metal element, the characteristic peak of ultraviolet light of the nano silver per se in the 400nm light wave range is fully exerted, the light protection of the traditional cerium oxide in the ultraviolet light wave range is realized, the comprehensive blue light resisting performance is greatly improved, and the concentration is 0.2mg.mL -1 When the ultraviolet absorption is carried out on short-wave blue light, the average transmittance is 0.24% in the wavelength range of 400-450nm, the ultraviolet absorbance is 2.17 in the range of 280-400nm of UVA and UVB bands, and the highest absorption peak absorbance is about 2.34.
3. The invention solves the problems of harm to skin, eyes and the like caused by short-wave blue light, greatly solves the defect that the traditional physical sun-screening material cannot screen light aging caused by short-wave blue light due to limited screening wavelength, also exerts the antibacterial property of nano silver, reduces the addition and use of preservative in related products, has the sterilizing rate of 82.05 percent for gram-positive bacteria under a 1.2% (W/V) system, and has obvious antibacterial effect in antibacterial test.
The foregoing is a summary of the invention and is further defined by the following detailed description of the invention when read in conjunction with the accompanying drawings.
Drawings
FIG. 1 shows cerium oxide (CeO) of an embodiment 2 ) Surface-modified cerium oxide (CeO) 2 -FTIR infrared spectrum schematic of PEI);
FIG. 2 shows a surface-modified cerium oxide (CeO) of an embodiment 2 -PEI) X-ray diffraction pattern;
FIG. 3 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI) X-ray energy spectrum;
FIG. 4 is a graph showing the relationship between the modified cerium oxide and the ultraviolet absorbance of various amounts of Polyethyleneimine (PEI) according to the examples;
FIG. 5 shows the preparation of a blue light-resistant cerium oxide-based sunscreen material (Ag NPs@CeO) from various amounts of L-ascorbic acid (L-AC) 2 -PEI) versus uv absorbance;
FIG. 6 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI) is made into a coating for visual blue light proof evidence schematic;
FIG. 7 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI）、CeO 2 -comparative schematic of the bactericidal effect of PEI and untreated cerium oxide on gram positive bacteria;
FIG. 8 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI）、CeO 2 -comparative schematic of the bacteriostatic effect of PEI and of cerium oxide without any treatment on gram-positive bacteria;
FIG. 9 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI) a schematic diagram of the centrifugal stability test of the sun protection product prepared by adding to the cosmetic formulation;
FIG. 10 shows an example of a cerium oxide-based blue-light resistant sunscreen material (Ag NPs@CeO) 2 -PEI).
Detailed Description
In order to make the objects and technical solutions and advantages of the present invention more apparent, the following detailed description is made with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a cerium oxide-based sun-screening material capable of resisting blue light, which is prepared by a preparation method comprising the following steps:
s1, dissolving 5g of cerium nitrate hexahydrate in 15ml of absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution A;
s2, dissolving 0.25g of polyethyleneimine in 10ml of absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution B;
s3, slowly adding the solution B into the solution A until a large amount of white floccules appear, adding 9.1711g of triethylamine, and reacting for a certain time t 1 I.e. 40 min, adding 350ml pure water by water cooling, and continuously cooling for a certain time t 2 I.e. 5 min, then hydrolyzing at room temperature for a certain time t 3 Namely, 1h, to obtain suspension C;
s4, washing the suspension C to be neutral by pure water, further centrifugally washing the suspension C by absolute ethyl alcohol and pure water for 3 times, drying the suspension C at 105 ℃ for 2 hours, and grinding the suspension C to obtain solid powder E;
s5, dispersing 0.3g of solid powder E in 10ml of pure water by ultrasonic, and dripping 5-6 drops of 2V/V% ammonia water to obtain turbid liquid F;
s6, adding 3mg/ml of silver-ammonia solution H5 ml into the turbid liquid F, performing light-shielding treatment, and reacting for a certain time t 4 Namely, after 15 min, 0.1mol/l L-ascorbic acid aqueous solution G0.4 ml is rapidly added under high-speed stirring of 1200rad/min, and the rotation speed is changed to 540rad/min to react for a certain time t at room temperature 5 I.e. 3 hours to obtain turbid liquid I;
s7, filtering the turbid liquid I to obtain a gray brown precipitate, respectively washing with absolute ethyl alcohol and pure water for 3 times, and drying at 105 ℃ for 2 hours to obtain gray brown powder (Ag NPs@CeO) 2 -PEI) to obtain the cerium oxide-based sun-screening material capable of resisting blue light.
As can be seen from FIG. 1, ceO 2 PEI at 3500-3000cm -1 The broad peak at this position is assigned to the primary amine bond in PEI, which indicates CeO 2 PEI contains not only associated NH 2 The structure is also provided with an NH structure; 1600cm -1 The absorption peak is NH bending vibration peak of primary amine and secondary amine; 1140cm -1 And 1100cm -1 The C-N stretching vibration peak of primary amine and secondary amine is at 1050cm -1 The absorption peak at this point is indicative of CeO 2 The presence of tertiary amine structures in PEI, the phenomenon of infrared spectrum illustrates CeO 2 The surface has been enriched with PEI polymer, confirming the presence of PEI.
As can be seen from FIG. 2, ceO 2 Reduction of the characteristic peak of PEI in X-ray diffraction (XRD) by oneHalf, the refractive crystal faces of (111), (220), (311), (331) are reserved relative to the cerium oxide PDF#43-1002 standard card. The combination of the infrared spectrum shows that the characteristic refraction angle of the cerium oxide surface is changed due to the enrichment of the surface with the polyethyleneimine, and further proves that the polyethyleneimine is successfully present on the cerium oxide surface.
As can be seen from FIG. 3, ag NPs@CeO 2 PEI in X-ray energy Spectroscopy (EDS), the appearance of characteristic peaks of silver element proves CeO 2 PEI successfully loads nano silver on an amino group.
Example 2
The embodiment provides a cerium oxide-based sun-screening material capable of resisting blue light, which is prepared by a preparation method comprising the following steps of:
0.50g of Polyethyleneimine (PEI) is dissolved in 10mL of absolute ethyl alcohol, and stirred to be fully dissolved, so as to obtain solution B;
as can be seen from FIG. 4, 5 experiments were conducted showing the relationship between the ultraviolet absorbance of CeO2-PEI obtained by modifying polyethyleneimine PEI at different concentrations, and the concentrations of polyethyleneimine used were 2.50%, 5.00%, 7.50% and 10.00%, respectively. The UV spectra were all at the same concentration (0.2 mg ∙ mL) -1 ) The measured graph shows that with the increase of the PEI dosage, the absorption condition at the 450nm short wave blue light shows a trend of decreasing first and then increasing, and the absorption condition in the UVA and UVB ranges shows a trend of increasing first and then decreasing, so that the ultraviolet and blue light resisting performance is good.
Example 3
The present example provides a cerium oxide-based sun-screening material that is resistant to blue light, prepared by a preparation method comprising the following steps, which is a specific step of changing the concentration of L-ascorbic acid (L-AC) as compared with example 1:
s5, dispersing 0.3g of solid powder E in 10ml of pure water by ultrasonic, and dripping 5-6 drops of 2V/V% ammonia water to obtain turbid liquid F;
s6, adding 3mg/ml of silver-ammonia solution H5 ml into the turbid liquid F, carrying out light-shielding treatment, and reactingTime t 4 Namely, after 15 min, 0.1mol/l L-ascorbic acid aqueous solution G0.5 ml is rapidly added under high-speed stirring of 1200rad/min, and the rotation speed is changed to 540rad/min to react for a certain time t at room temperature 5 I.e. 3 hours to obtain turbid liquid I;
s7, filtering the turbid liquid I to obtain a gray brown precipitate, respectively washing with absolute ethyl alcohol and pure water for 3 times, and drying at 105 ℃ for 2 hours to obtain gray brown powder (Ag NPs@CeO) 2 -PEI) to obtain the cerium oxide-based sun-screening material capable of resisting blue light.
As can be seen from FIG. 5, L-AC and CeO are shown 2 7 sets of experiments were set up with respect to UV absorbance for different mass ratios of PEI (PEI: 5%), with amounts of L-AC of 0.588%, 1.174%, 1.761%, 2.348%, 2.935%, respectively. The UV spectra were all at the same concentration (0.2 mg ∙ mL) -1 ) As shown in the following measurement, the absorbance in the short-wave blue light region showed a tendency of increasing and decreasing, and when the L-AC amount was 2.348%, the absorbance was optimal for the short-wave blue light region, and the L-AC amount in the experiment was 2.348%, ceO after modification 2 The absorbance of short wave blue light is higher than before unmodified.
As can be seen from FIG. 6, ag NPs@CeO prepared in example 1 was taken 2 PEI samples were made as a coating, with 4 letter "GDPU" in the figure covered with 3, 2, 1 and 0 layers of sun protection material, respectively, and visually demonstrated against blue light using commercially approved blue light protection test cards. It can be seen that Ag NPs@CeO 2 The coating made of PEI has excellent blue light resistance.
As can be seen from FIG. 7, ag NPs@CeO prepared in example 1 was taken 2 PEI sample and CeO prepared in example 2 2 PEI and cerium oxide without any treatment. Through sterilization experiments, ag NPs@CeO can be known 2 The sterilization performance of PEI is obviously increased, the sterilization rate of 1.2% (W/V) to gram-positive bacteria reaches 82.05%, and the sterilization rate reaches 100% under the light synergistic effect.
As can be seen from FIG. 8, ag NPs@CeO prepared in example 1 was taken 2 PEI sample and CeO prepared in example 2 2 PEI, and cerium oxide without any treatment. Through bacteriostasis experiments, the composition canAg NPs@CeO is known 2 The PEI sample has obvious antibacterial effect on gram-positive bacteria after silver loading.
The sterilizing effect can directly or indirectly reduce the addition and use of partial preservative used in cosmetics, thereby comprehensively reducing the cost and improving the antiseptic property.
Example 4
Taking 0.6g of cerium oxide-based sun-screening material sample (Ag NPs@CeO2-PEI) capable of resisting blue light of example 1 as 1.2% sun-screening cream, and performing a centrifugal speed of 3000 rad/min and a centrifugal stability test of 30min on the product by referring to QB/T1857-2013 skin cream, wherein the test result is shown in figure 9 2 The PEI is uniformly dispersed in the cosmetic product, and no layering and other conditions appear, which indicates Ag NPs@CeO 2 PEI has good compounding property and can be directly used as a novel sun-screening material to be directly added for use; the observation of the sample of the cerium oxide-based sun-screening material of example 1, which is resistant to blue light, by using an SEM Scanning Electron Microscope (SEM), shows that the overall morphology is nearly spherical as shown in fig. 10, and the sample has a relatively high specific surface area, so that short-wave blue light and ultraviolet light can be effectively screened.
Detailed description of the invention the present invention is directed to a process for preparing cerium nitrate hexahydrate
（Ce（NO 3 ） 3 ·6H 2 O) and silver Nitrate (NS), and cerium oxide (CeO) is obtained by promoting precipitation reaction with Triethylamine (TEA) 2 ) The dendritic Polyethylenimine (PEI) is used as a template agent for synthesis to obtain a primary product CeO 2 PEI, then reducing its silver particles by L-ascorbic acid (L-AC), and making CeO by complexation reaction 2 Silver is carried on the surface of PEI to prepare the cerium oxide-based sun-proof material (Ag NPs@CeO) capable of resisting blue light 2 -PEI). Meanwhile, the spherical morphology obtained by SEM observation is favorable for light refraction and absorption, and has higher specific surface area and is more favorable for resisting blue light and ultraviolet rays. The FTIR pattern and XRD pattern are used to prove the success of PEI and cerium oxide CeO 2 Compounding together; demonstration of CeO Using EDS Picture 2 -PEI successfully loads the silver element; the UV spectrum is used for measuring that the sun-screening material has higher absorptionLuminosity, thus has the effects of resisting blue light and ultraviolet rays; the blue light resisting performance of the material is further verified by using a blue light resisting test card approved in the market; the antibacterial and bactericidal experimental data prove that the sun-screening material for resisting blue light has a certain antibacterial effect.
Variations and modifications of the above embodiments, such as any of the constituent Polyethylenimine (PEI), cerium nitrate hexahydrate (Ce (NO) 3 ） 3 6H 2O), silver Nitrate (NS), triethylamine (TEA), etc., to form different samples, the examples of the present invention are not exhaustive of all the ratios, but any modifications based on experimental principles in the examples of the present invention are not limited to the above-disclosed and described embodiments, and any modifications and variations of the present invention should also fall within the scope of the claims of the present invention.
Claims (3)
1. A ceria-based sun protection material that is resistant to blue light, comprising: polyethyleneimine, triethylamine, cerium nitrate hexahydrate, L-ascorbic acid, silver nitrate; the molar ratio of the polyethyleneimine to the cerium nitrate hexahydrate is 2-4:1-10; the molar ratio of the triethylamine to the cerium nitrate hexahydrate is 5-20:1-200; the molar ratio of the L-ascorbic acid to the cerium nitrate hexahydrate is 1-2:120-600; the molar ratio of the silver nitrate to the cerium nitrate hexahydrate is 1-2:100-250;
the preparation method of the cerium oxide-based sun-screening material capable of resisting blue light comprises the following steps:
s1, dissolving cerium nitrate hexahydrate in absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution A;
s2, dissolving polyethyleneimine in absolute ethyl alcohol, and stirring to fully dissolve to obtain a solution B;
s3, slowly adding the solution B into the solution A until a large amount of white floccules appear, adding triethylamine, and reacting for a certain time t 1 Water cooling, adding pure water for hydrolysis reaction, and continuously coolingTime t 2 After which the reaction is carried out at room temperature for a certain time t 3 Obtaining a suspension C;
s4, washing the suspension C to be neutral by pure water, further centrifugally washing by absolute ethyl alcohol and pure water, drying and grinding to obtain solid powder E;
s5, dispersing the solid powder E in pure water by ultrasonic, and dripping 2V/V% ammonia water to obtain turbid liquid F;
s6, adding the silver ammonia solution H into the turbid liquid F, performing light-shielding treatment, and reacting for a certain time t 4 Then adding L-ascorbic acid aqueous solution G under high-speed stirring, changing the rotating speed, and reacting for a certain time t at room temperature 5 Obtaining turbid liquid I;
s7, carrying out suction filtration on the turbid liquid I to obtain a gray brown precipitate, respectively washing with absolute ethyl alcohol and pure water, and drying to obtain gray brown powder, thus obtaining the cerium oxide-based sun-screening material capable of resisting blue light;
the concentration of the solution A is 30W/V-50W/V;
the concentration of the solution B is 2.5W/V-10W/V;
reaction time t in step S3 1 For 20-60 min, cooling time t 2 1-15 min, reaction time t at room temperature 3 1-4 h;
the concentration of the solid powder E in the step S5 is 1-10W/V%;
the step S6 further includes:
dissolving L-ascorbic acid in pure water, and stirring thoroughly to obtain L-ascorbic acid aqueous solution G, wherein the concentration of the L-ascorbic acid aqueous solution is 2-5W/V%;
reaction time t in step S6 4 The high-speed stirring is carried out for 10-30 min at a rotating speed of 1000-2000 rad/min for 1-5 min, and the room temperature reaction time t is changed at a rotating speed of 400-600 rad/min 5 2-10 h.
2. The ceria-based blue light resistant sunscreen material of claim 1, further comprising in step S6:
dissolving silver nitrate in pure water, stirring thoroughly, and dripping 2V/V% ammonia water to obtain silver ammonia solution H with concentration of 0.1-0.5W/V%.
3. The blue light resistant ceria-based sunscreen material of claim 1 wherein said step S4 and step S7 are both drying conditions of 1-3h at 95-115 ℃.
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