CN110527230A - A kind of ultraviolet-resistant ternary nano composite film material and preparation method thereof - Google Patents
A kind of ultraviolet-resistant ternary nano composite film material and preparation method thereof Download PDFInfo
- Publication number
- CN110527230A CN110527230A CN201910775588.0A CN201910775588A CN110527230A CN 110527230 A CN110527230 A CN 110527230A CN 201910775588 A CN201910775588 A CN 201910775588A CN 110527230 A CN110527230 A CN 110527230A
- Authority
- CN
- China
- Prior art keywords
- ultraviolet
- film material
- composite film
- nano composite
- ternary nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000012460 protein solution Substances 0.000 claims abstract description 26
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 230000003292 diminished effect Effects 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- -1 are adjusted pH Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 5
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 108010055615 Zein Proteins 0.000 claims description 12
- 229920002494 Zein Polymers 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 108010061711 Gliadin Proteins 0.000 claims description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 108010050792 glutenin Proteins 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims 2
- 108010073771 Soybean Proteins Proteins 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000000419 plant extract Substances 0.000 claims 1
- 235000019710 soybean protein Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 30
- 210000004027 cell Anatomy 0.000 description 18
- 238000002386 leaching Methods 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 9
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000002314 glycerols Chemical class 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000001339 epidermal cell Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000004040 pyrrolidinones Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 230000003833 cell viability Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008685 targeting Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 101710094902 Legumin Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012930 cell culture fluid Substances 0.000 description 1
- 239000006143 cell culture medium Substances 0.000 description 1
- 238000013043 cell viability test Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NEKNNCABDXGBEN-UHFFFAOYSA-L disodium;4-(4-chloro-2-methylphenoxy)butanoate;4-(2,4-dichlorophenoxy)butanoate Chemical compound [Na+].[Na+].CC1=CC(Cl)=CC=C1OCCCC([O-])=O.[O-]C(=O)CCCOC1=CC=C(Cl)C=C1Cl NEKNNCABDXGBEN-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000006481 glucose medium Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of ultraviolet-resistant ternary nano composite film material and preparation method thereof, the ultraviolet-resistant ternary nano composite film material, including albumen, nano-cerium oxide, dispersing agent and surfactant；The preparation method comprises the following steps: (1) by protein dissolution in solvent A, obtaining protein solution；(2) cerium source, urea and dispersing agent are sequentially added into protein solution, are adjusted pH, surfactant are then added, heating stirring obtains composite solution；(3) composite solution is filtered under diminished pressure, is dried in vacuo, obtains ultraviolet-resistant ternary nano composite film material.Ultraviolet-resistant ternary nano composite film material transparency prepared by the present invention is higher, has very strong ultraviolet screening ability, and have good hygroscopicity and biocompatibility.
Description
Technical field
The invention belongs to macromolecule organic-inorganic nano particle compounding technologies to synthesize composite membrane field, be related to a kind of ultraviolet
Obstruct ternary nano composite film material and preparation method thereof.
Background technique
Cerium oxide is most one of active rare earth oxide of chemical property, has high refractive index and in limit of visible spectrum
There is very high transparency, meanwhile, it can also resist ultraviolet light and can store a large amount of oxygen.Compare Zn0, for TiO2,
While keeping powerful ultraviolet absorption ability, CeO2Optical clarity after film forming can be better than Zn0, TiO2,Therefore nano oxygen
Change the research interest that cerium causes people powerful in the fields such as uvioresistant coating material and sunscreen product.
The influence factor for influencing nano-cerium oxide ultraviolet-resistant performance is mainly its particle size, degree of scatter, Yi Jiwen
It is qualitative.The method of numerous studies report synthesis nano-cerium oxide such as alcohol heating method, hydro-thermal method, the precipitation method, sol-gal process, is sprayed
Pyrolysismethod.The nano-cerium oxide partial size that the above method obtains reduces, and chemical homogeneity is higher, and purity improves, but there is also
Some disadvantages, usually pressure required for these methods, temperature, the requirement of equipment is all very high, and cost is higher, and some even can be right
Environment pollutes.Wherein in-situ sol-gel uses the mechanism of fabricated in situ, and it is directly former that chemical reaction occurs on substrate
Position synthesis of metal oxide functive, at the same time because it is there are chemical bond complexing between metal oxide and high molecular material, because
This nano particle diameter is smaller, is supported on stable structure on macromolecule, well dispersed, is before having very much in current materials synthesis technique
The mode of scape.
Chinese patent 201110153710.4 discloses a kind of imitative ceramic flexible nano compound film material of highly-transparent ultraviolet-resistant
Material and preparation method thereof, composite film material use phase transfer-situ aggregation method, and preparation process is more complex, it is seen that light transmittance
Reach 90% or more, rate of ultraviolet shield reaches 99% or more.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of ultraviolet-resistant ternary nano compound film material
Material and preparation method thereof.Nano composite membrane material transparent degree prepared by the present invention is higher, has very strong ultraviolet screening ability,
And there is good hygroscopicity and biocompatibility.
The purpose of the present invention is realized at least by one of following technical scheme.
The present invention provides a kind of ultraviolet-resistant ternary nano composite film material, the component including following mass percent:
The albumen of 24.2-49.7wt%, the nano-cerium oxide of 0.65-3.1wt%, 49.7-72.6 wt% dispersing agent and 4.5-8.7 wt
The surfactant of %.
Preferably, the albumen is extracted form natural plant albumen, and extracted form natural plant albumen includes zeins, big
One or more of legumin glutenin, gliadin.
Preferably, the dispersing agent is water soluble polymer, and the water soluble polymer contains carbonyl or carboxyl, water-soluble
Macromolecule includes one or more of polyvinylpyrrolidone, polyacrylic acid, maleic anhydride.
Preferably, surfactant includes glycerol, Tween-80, one or more of Arlacel-20.
The present invention also provides the methods for preparing the ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) by protein dissolution in solvent A, protein solution is obtained；
(2) cerium source, urea and dispersing agent are sequentially added into protein solution, are adjusted pH, surfactant are then added, heating is stirred
It mixes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, is dried in vacuo, obtains ultraviolet-resistant ternary nano composite film material.
Preferably, it is that albumen is added in 60-80 DEG C of solvent A by the condition of protein dissolution in step (1), then exists
60-80 DEG C is continued to be heated to reflux stirring 15-30 minutes；
The quality of albumen and the volume ratio of solvent A are 10-12 mg/mL；
The acetone that the solvent A is the ethyl alcohol that volume fraction is 65%-90% or volume fraction is 70%-80%.
Preferably, cerium source, urea and dispersing agent is added in step (2) into protein solution, adjusts pH, surface is then added
When activating agent, the temperature of protein solution is 60-80 DEG C；The heating stirring is return stirring 15-20 minutes at 60-80 DEG C
Afterwards, it is warming up to 80-100 DEG C, and is persistently stirred at 80-100 DEG C 2-5 minutes.
Preferably, cerium source is cerous salt in step (2), and cerium source includes six nitric hydrate ceriums, cerous chloride, hydration carbonic acid
One or more of cerium；Cerium source, albumen, urea, dispersing agent and surfactant mass ratio be 1:(3-30): (1-2): (9-
90): (1-1.5).
Preferably, the pH adjusted in step (2) is 8-9；Adjustment pH used in compound include sodium hydroxide, sodium carbonate,
One or more of ammonium hydroxide.
Preferably, vacuum drying temperature is 80-100 DEG C in step (3), and the vacuum drying time is 12-24 hours.
Compared to the prior art, the invention has the advantages that and advantage:
(1) zein/pvp/CeO provided by the invention2Tri compound hybridized film, that is, ultraviolet-resistant ternary nano composite film material, shape
At nano particle be uniformly dispersed, partial size is small, while improving the hygroscopicity of composite membrane, has both played cerium oxide superior UV barrier
Performance, and control the toxicity of nanoparticle；
(2) preparation method provided by the invention is using original position-sol-gal process, and the method is simple, and simple process is easy；
(3) ultraviolet-resistant ternary nano composite film material provided by has very strong ultraviolet screening ability, in UVA(320-
400nm) rate of ultraviolet shield be 80.1-89.8%, in UVB(275-320nm) rate of ultraviolet shield be 90.8-98.2%, in UVC
(200-275nm) rate of ultraviolet shield is 98.2-100.0%, and has good hygroscopicity and biocompatibility, is expected to apply
In fields such as construction uvioresistant device, the sun-proof, food packagings of cosmetics.
Detailed description of the invention
Fig. 1 is nano-cerium oxide partial size and pure corn in the ultraviolet-resistant ternary nano composite film material of the preparation of embodiment 3
The grain-size graph of albumen；
Fig. 2 is that nano-cerium oxide disperses TEM figure in the ultraviolet-resistant ternary nano composite film material of the preparation of embodiment 1；
Fig. 3 is the transmissivity of the ultraviolet-resistant ternary nano composite film material of different cerium sources content prepared by embodiment 1 to 5；
Fig. 4 is the ultraviolet-resistant ternary nano composite film material leaching liquor culture of the different cerium sources content prepared in embodiment 1 to 4
Hacat cells cell viability performance；
Fig. 5 a and Fig. 5 b are the ultraviolet-resistant ternary nano composite membrane leaching liquor of the different cerium sources content prepared in embodiment 1 to 4
The karyomorphism of the Hacat cells of culture, wherein Fig. 5 a is the karyomorphism for having cultivated Hacat cells for 24 hours, figure
5b has cultivated the karyomorphism of the Hacat cells of 48h；
Fig. 6 is the suction of the ultraviolet-resistant ternary nano composite film material of different pvp contents prepared by embodiment 3 and embodiment 6 to 8
Wet performance.
Specific embodiment
Specific implementation of the invention is described further below in conjunction with specific embodiments and the drawings, but implementation of the invention
It is without being limited thereto.
Embodiment 1
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) 20 mg, six nitric hydrate cerium, 24 mg urea and 1.8 g polyethylene are sequentially added into protein solution at 60 DEG C
Pyrrolidones adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s, In is then added
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at 60 DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material, i.e. composite membrane -1 are obtained.
Embodiment 2
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) 50 mg, six nitric hydrate cerium, 60 mg urea and 1.8g polyethylene pyrrole are sequentially added into protein solution at 60 DEG C
Pyrrolidone adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s is then added, 60
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -2 is obtained.
Embodiment 3
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) 100 mg, six nitric hydrate cerium, 120 mg urea and the poly- second of 1.8 g are sequentially added into protein solution at 60 DEG C
Alkene pyrrolidone adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s is then added,
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at 60 DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -3 is obtained.
Embodiment 4
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) 200 mg, six nitric hydrate cerium, 240 mg urea and the poly- second of 1.8 g are sequentially added into protein solution at 60 DEG C
Alkene pyrrolidone adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s is then added,
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at 60 DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -4 is obtained.
Embodiment 5(comparative example)
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) six nitric hydrate cerium of 0mg, 0 mg urea and 1.8g polyvinyl pyrrole are sequentially added into protein solution at 60 DEG C
Alkanone adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s is then added, at 60 DEG C
Lower return stirring is warming up to 80 DEG C and persistently stirs 2 minutes after 15 minutes, obtain composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -5 is obtained.
Embodiment 6
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) six nitric hydrate cerium of 100mg, 120 mg urea and 0 g polyethylene pyrrole are sequentially added into protein solution at 60 DEG C
Pyrrolidone adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s is then added, 60
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -6 is obtained.
Embodiment 7
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) six nitric hydrate cerium of 100mg, 120 mg urea and 0.6 g polyethylene are sequentially added into protein solution at 60 DEG C
Pyrrolidones adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s, In is then added
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at 60 DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -7 is obtained.
Embodiment 8
Present embodiments provide a kind of method for preparing ultraviolet-resistant ternary nano composite film material, comprising the following steps:
(1) at 60 DEG C by 600mg zeins be substantially dissolved in 50 ml volume fractions be 75% ethanol water in,
It is heated to reflux stirring 15 minutes at 60 DEG C, obtains protein solution；
(2) six nitric hydrate cerium of 100mg, 120 mg urea and 1.2g polyethylene are sequentially added into protein solution at 60 DEG C
Pyrrolidones adjusts pH to 8 with the sodium hydroxide solution of 1mol/L, 100 μ L glycerols and 100 μ L Tween-80s, In is then added
Return stirring is warming up to 80 DEG C and persistently stirs 2 minutes at 60 DEG C after 15 minutes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, obtains film forming solution, film forming solution is evenly coated on glass slide, the vacuum at 80 DEG C
After 24 hours dry, ultraviolet-resistant ternary nano composite film material i.e. composite membrane -8 is obtained.
Fig. 1 is nano-cerium oxide partial size and pure corn in the ultraviolet-resistant ternary nano composite film material of the preparation of embodiment 3
The grain-size graph of albumen.The film forming solution that embodiment 3 prepares is taken into a small amount of progress partial size test, resulting nano particle diameter is
164nm or so, and the partial size of pure zeins is 106nm or so, the partial size of gained film forming solution is increased slightly, it was demonstrated that at
There is new nanoparticle to generate in coating solution, i.e. nano-cerium oxide.
Fig. 2 is that nano-cerium oxide disperses TEM figure in the ultraviolet-resistant ternary nano composite film material of the preparation of embodiment 1.
The film forming solution for taking a small amount of embodiment 1 to prepare carries out transmission electron microscopy test, it can be seen that prepared sample
Product, nano-cerium oxide (black color dots) are uniformly dispersed, and partial size is 80nm or so.
Fig. 3 is the transmission of the ultraviolet-resistant ternary nano composite film material of different cerium sources content prepared by embodiment 1 to 5
Rate；It is prepared by embodiment 1-4 ultraviolet-resistant ternary nano composite film material (i.e. composite membrane -1, composite membrane -2, composite membrane -3 and
Composite membrane -4) ultraviolet transmission test is carried out, compared with the composite membrane -5 of control group (embodiment 5), there is very strong ultraviolet screen
Ability is covered, in UVA(320-400nm) rate of ultraviolet shield be 80.1-89.8%, in UVB(275-320nm) rate of ultraviolet shield
For 90.8-98.2%, in UVC(200-275nm) rate of ultraviolet shield is 98.2-100.0%, and with the increasing of cerium source content
Add, ultraviolet shielded rate also will increase, while keep preferable light transmittance.
Fig. 4 is the ultraviolet-resistant ternary nano composite film material leaching liquor of the different cerium sources content prepared in embodiment 1 to 4
The cell viability performance of the HaCaT cells of culture.1mL mixes 10% serum and 1% dual anti-shape with DMEM high glucose medium
At cell culture fluid, composite membrane -1, composite membrane -2, composite membrane -3, composite membrane -4 respectively take 1mg, the cell culture are respectively added
In liquid, it is totally submerged composite membrane, liquid is crossed into 0.22 micron membrane filter after placing 24 hours in 37 degree of incubators, forms extraction
Liquid -1, leaching liquor -2, leaching liquor -3, leaching liquor -4 after cell extracts for 24 hours in each leaching liquor, carry out cell viability test, can
To see that, by culture for 24 hours, (control group is the cell culture medium for being added without composite membrane, is cultivated completely with DMEM with control group
Base normally cultivates cell, does not do other processing) it compares, there is significant difference, it is thin that people immortalizes epidermal cell (HaCaT cells)
Good vigor is presented in born of the same parents.(* indicates that P < 0.05, * * indicate that P < 0.01, * * * indicate P < 0.001)
Fig. 5 a and Fig. 5 b are the ultraviolet-resistant ternary nano composite film material leaching of the different cerium sources content prepared in embodiment 1 to 4
The karyomorphism of the HaCaT cells of extract culture, wherein Fig. 5 a is the cell karyomorphism for having cultivated HaCaT cells for 24 hours
State, Fig. 5 b are the karyomorphism for having cultivated the HaCaT cells of 48h；
Nuclear targeting is carried out afterwards for 24 hours with above-mentioned leaching liquor culture cell, it can be seen that people immortalizes epidermal cell (HaCaT
Cells nucleus) compares, and (control group is that composite membrane culture medium is not added to control group, is normally cultivated with DMEM complete medium
Cell does not do other processing) for, there is no shrinkages for karyomorphism, are crushed, sharpness of border, form is complete.Illustrate to implement
Ultraviolet-resistant ternary nano composite film material prepared by example 1 to 4 does not have toxicity to cell, and biocompatibility is good.
With nuclear targeting is carried out after above-mentioned leaching liquor culture cell 48h, by the cell culture of 48h, it can be seen that can
It is compared for control group with seeing that people immortalizes the nucleus of epidermal cell (HaCaT cells), karyomorphism is not sent out
Raw shrinkage, is crushed, sharpness of border, and form is complete.Illustrate ultraviolet-resistant ternary nano compound film material prepared by embodiment 1 to 4
The processing to the cell long period is expected also without toxicity, and biocompatibility is good.
Fig. 6 is the ultraviolet-resistant ternary nano composite film material of different pvp contents prepared by embodiment 3 and embodiment 6 to 8
Moisture pick-up properties, i.e., by composite membrane -3, composite membrane -6, composite membrane -7, composite membrane 8 carry out hygroscopicity test, it can be seen that pass through
After for 24 hours, with the increase of polyvinyl pyrrolidone content, the hydroscopicity of composite membrane is consequently increased, and is greatly improved compound
The hygroscopicity of film.
The foregoing is only a preferred embodiment of the present invention, not does restriction in any form to the present invention.It is all
Any equivalent variation that those skilled in the art makes above-described embodiment using technical solution of the present invention is modified or is drilled
Become etc., all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of ultraviolet-resistant ternary nano composite film material, which is characterized in that the component including following mass percent:
The albumen of 24.2-49.7wt%, the nano-cerium oxide of 0.65-3.1wt%, 49.7-72.6 wt% dispersing agent and 4.5-8.7 wt
The surfactant of %.
2. ultraviolet-resistant ternary nano composite film material according to claim 1, which is characterized in that the albumen is natural
Plant extract albumen, extracted form natural plant albumen include zeins, soybean protein glutenin, in gliadin
More than one.
3. ultraviolet-resistant ternary nano composite film material according to claim 1, which is characterized in that the dispersing agent is water
Soluble macromolecular, the water soluble polymer contain carbonyl or carboxyl, and water soluble polymer includes polyvinylpyrrolidone, poly- third
One or more of olefin(e) acid, maleic anhydride.
4. ultraviolet-resistant ternary nano composite film material according to claim 1, which is characterized in that surfactant includes
Glycerol, Tween-80, one or more of Arlacel-20.
5. the method for preparing the ultraviolet-resistant ternary nano composite film material as described in any one of Claims 1-4, feature exist
In, comprising the following steps:
(1) by protein dissolution in solvent A, protein solution is obtained；
(2) cerium source, urea and dispersing agent are sequentially added into protein solution, are adjusted pH, surfactant are then added, heating is stirred
It mixes, obtains composite solution；
(3) composite solution is filtered under diminished pressure, is dried in vacuo, obtains ultraviolet-resistant ternary nano composite film material.
6. the method according to claim 5 for preparing ultraviolet-resistant ternary nano composite film material, which is characterized in that step
(1) in then the condition of protein dissolution is continued to be heated to reflux for albumen to be added in 60-80 DEG C of solvent A at 60-80 DEG C
Stirring 15-30 minutes；
The quality of albumen and the volume ratio of solvent A are 10-12 mg/mL；
The acetone that the solvent A is the ethyl alcohol that volume fraction is 65%-90% or volume fraction is 70%-80%.
7. the method according to claim 5 for preparing ultraviolet-resistant ternary nano composite film material, which is characterized in that step
(2) cerium source, urea and dispersing agent is added in into protein solution, adjusts pH, when surfactant is then added, protein solution
Temperature is 60-80 DEG C；The heating stirring be warming up to 80-100 DEG C at 60-80 DEG C after return stirring 15-20 minutes, and
It is persistently stirred at 80-100 DEG C 2-5 minutes.
8. the method according to claim 5 for preparing ultraviolet-resistant ternary nano composite film material, which is characterized in that step
(2) cerium source is cerous salt in, and cerium source includes one or more of six nitric hydrate ceriums, cerous chloride, cerium carbonate hydrate；Cerium
Source, albumen, urea, dispersing agent and surfactant mass ratio be 1:(3-30): (1-2): (9-90): (1-1.5).
9. the method according to claim 5 for preparing ultraviolet-resistant ternary nano composite film material, which is characterized in that step
(2) pH adjusted in is 8-9；Adjusting compound used in pH includes one or more of sodium hydroxide, sodium carbonate, ammonium hydroxide.
10. the method according to claim 5 for preparing ultraviolet-resistant ternary nano composite film material, which is characterized in that step
Suddenly vacuum drying temperature is 80-100 DEG C in (3), and the vacuum drying time is 12-24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910775588.0A CN110527230B (en) | 2019-08-21 | 2019-08-21 | Ultraviolet-blocking ternary nano composite film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910775588.0A CN110527230B (en) | 2019-08-21 | 2019-08-21 | Ultraviolet-blocking ternary nano composite film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110527230A true CN110527230A (en) | 2019-12-03 |
| CN110527230B CN110527230B (en) | 2022-02-15 |
Family
ID=68663948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910775588.0A Active CN110527230B (en) | 2019-08-21 | 2019-08-21 | Ultraviolet-blocking ternary nano composite film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110527230B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292523A (en) * | 2021-12-03 | 2022-04-08 | 华南理工大学 | Tea polyphenol cross-linked nano cerium oxide-embedded protein/polysaccharide composite membrane material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| CN108324701A (en) * | 2018-03-05 | 2018-07-27 | 西北师范大学 | A kind of pH sensibility zein group compound film and preparation method thereof |
-
2019
- 2019-08-21 CN CN201910775588.0A patent/CN110527230B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| CN108324701A (en) * | 2018-03-05 | 2018-07-27 | 西北师范大学 | A kind of pH sensibility zein group compound film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HONG WEI HE等: "Synthesis of crystalline cerium dioxide hydrosol by a sol–gel method", 《CERAMICS INTERNATIONAL》 * |
| PARWAIZ, SHAI等: "CeO2-based nanocomposites: An advanced alternative to TiO2 and ZnO in sunscreens", 《MATERIALS EXPRESS》 * |
| 曲亮璠: "zein/纳米TiO2/CS复合膜的制备及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292523A (en) * | 2021-12-03 | 2022-04-08 | 华南理工大学 | Tea polyphenol cross-linked nano cerium oxide-embedded protein/polysaccharide composite membrane material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110527230B (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ao et al. | Preparation and characterization of 1-naphthylacetic acid–silica conjugated nanospheres for enhancement of controlled-release performance | |
| CN103361885B (en) | A kind of preparation method of antibacterial fibroin fiber film | |
| CN110003896B (en) | Anti-oxidation cerium-doped carbon quantum dot and preparation method and application thereof | |
| CN103922314B (en) | Fluorescent carbon nanoparticles as well as preparation method and application thereof | |
| JP2011514883A (en) | Silver nanoparticles having specific surface area and method for producing the same | |
| Tang et al. | Development, structure characterization and stability of food grade selenium nanoparticles stabilized by tilapia polypeptides | |
| Nie et al. | Chameleon-inspired iridescent structural color textiles with reversible multiple stimulus-responsive functions | |
| CN112159342A (en) | Method for extracting astaxanthin from shrimp shells by using natural eutectic solvent of amino acids | |
| CN107502349B (en) | Preparation method of water-soluble bluish violet light carbon quantum dots | |
| Nagar et al. | Synthesis and characterization of silver nanoparticles via green route | |
| CN116654986B (en) | Manganese sulfide nanoflower integrated diagnosis and treatment preparation and preparation method and application thereof | |
| Jiang et al. | Fabrication of multifunctional fluorescent organic nanoparticles with AIE feature through photo-initiated RAFT polymerization | |
| Zang et al. | Design and site-directed compartmentalization of gold nanoclusters within the intrasubunit interfaces of ferritin nanocage | |
| CN110257060A (en) | Utilize the method and product of resveratrol preparation carbon dots and application | |
| CN110527230A (en) | A kind of ultraviolet-resistant ternary nano composite film material and preparation method thereof | |
| CN105478795A (en) | Method for preparing silver nanoparticles with sugarcane extract | |
| CN113523297A (en) | Method for preparing nano-silver by using peony extract | |
| CN107603610A (en) | Preparation method from mature vinegar carbon nano-particles | |
| CN110976908B (en) | Gold-platinum bimetallic nano-particles and preparation method thereof | |
| CN109593524A (en) | Use radiation loose wire preparation Water-soluble carbon quantum dot and the method and its application of fluorescent ink | |
| CN109187462A (en) | A kind of solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion and its preparation and application | |
| CN110669507B (en) | Preparation method and application of degradable non-stoichiometric cobalt sulfide nanodots | |
| CN114951681B (en) | Method for preparing platinum nanoparticles by adopting cordyceps flower extract | |
| CN112044287A (en) | Zinc complex modified cellulose acetate composite membrane and preparation method thereof | |
| CN110308126A (en) | A method of using chinaberry hinge at fluorescence nano carbon dots cell imaging |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230914 Address after: Room 3513, No. 372 Huanshi East Road, Yuexiu District, Guangzhou City, Guangdong Province, 510030 (multiple photos of one site) Patentee after: Guangzhou Bikang Biotechnology Co.,Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: SOUTH CHINA University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231213 Address after: Room 3513, No. 372, Huanshi East Road, Yuexiu District, Guangzhou, Guangdong, 510030 Patentee after: Guangzhou Zhiyuan Biotechnology Co.,Ltd. Address before: Room 3513, No. 372 Huanshi East Road, Yuexiu District, Guangzhou City, Guangdong Province, 510030 (multiple photos of one site) Patentee before: Guangzhou Bikang Biotechnology Co.,Ltd. |