CN113058667A - 一种人工类囊体微流控芯片及其制备方法与应用 - Google Patents
一种人工类囊体微流控芯片及其制备方法与应用 Download PDFInfo
- Publication number
- CN113058667A CN113058667A CN202110293147.4A CN202110293147A CN113058667A CN 113058667 A CN113058667 A CN 113058667A CN 202110293147 A CN202110293147 A CN 202110293147A CN 113058667 A CN113058667 A CN 113058667A
- Authority
- CN
- China
- Prior art keywords
- thylakoid
- artificial
- microfluidic chip
- layer structure
- micro
- 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
- 210000002377 thylakoid Anatomy 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 42
- 239000005515 coenzyme Substances 0.000 claims abstract description 32
- -1 nicotinoyl Chemical group 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 230000008929 regeneration Effects 0.000 claims abstract description 24
- 238000011069 regeneration method Methods 0.000 claims abstract description 24
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- 101000950981 Bacillus subtilis (strain 168) Catabolic NAD-specific glutamate dehydrogenase RocG Proteins 0.000 claims description 18
- 102000016901 Glutamate dehydrogenase Human genes 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 16
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 16
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 13
- 239000013473 2D covalent-organic framework Substances 0.000 claims description 13
- 238000007385 chemical modification Methods 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002096 quantum dot Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 4
- 102000004316 Oxidoreductases Human genes 0.000 abstract description 19
- 108090000854 Oxidoreductases Proteins 0.000 abstract description 19
- 102000004190 Enzymes Human genes 0.000 abstract description 6
- 108090000790 Enzymes Proteins 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 10
- BOPGDPNILDQYTO-NNYOXOHSSA-N nicotinamide-adenine dinucleotide Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 BOPGDPNILDQYTO-NNYOXOHSSA-N 0.000 description 9
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BAWFJGJZGIEFAR-NNYOXOHSSA-O NAD(+) Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-O 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229940049906 glutamate Drugs 0.000 description 3
- 229930195712 glutamate Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XJLXINKUBYWONI-DQQFMEOOSA-N [[(2r,3r,4r,5r)-5-(6-aminopurin-9-yl)-3-hydroxy-4-phosphonooxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [(2s,3r,4s,5s)-5-(3-carbamoylpyridin-1-ium-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl phosphate Chemical group NC(=O)C1=CC=C[N+]([C@@H]2[C@H]([C@@H](O)[C@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](OP(O)(O)=O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 XJLXINKUBYWONI-DQQFMEOOSA-N 0.000 description 2
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 2
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002989 glutamic acid Drugs 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- KPGXRSRHYNQIFN-UHFFFAOYSA-L 2-oxoglutarate(2-) Chemical compound [O-]C(=O)CCC(=O)C([O-])=O KPGXRSRHYNQIFN-UHFFFAOYSA-L 0.000 description 1
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical compound CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- 108010081996 Photosystem I Protein Complex Proteins 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012612 static experiment Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502715—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by interfacing components, e.g. fluidic, electrical, optical or mechanical interfaces
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/18—Apparatus specially designed for the use of free, immobilized or carrier-bound enzymes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/02—Form or structure of the vessel
- C12M23/16—Microfluidic devices; Capillary tubes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
- C12P13/14—Glutamic acid; Glutamine
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/26—Preparation of nitrogen-containing carbohydrates
- C12P19/28—N-glycosides
- C12P19/30—Nucleotides
- C12P19/36—Dinucleotides, e.g. nicotineamide-adenine dinucleotide phosphate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0809—Geometry, shape and general structure rectangular shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
- B01L2300/0883—Serpentine channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0887—Laminated structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/12—Specific details about materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/16—Surface properties and coatings
- B01L2300/168—Specific optical properties, e.g. reflective coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2400/00—Moving or stopping fluids
- B01L2400/04—Moving fluids with specific forces or mechanical means
- B01L2400/0403—Moving fluids with specific forces or mechanical means specific forces
- B01L2400/046—Chemical or electrochemical formation of bubbles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- Clinical Laboratory Science (AREA)
- Biotechnology (AREA)
- Analytical Chemistry (AREA)
- Hematology (AREA)
- Biomedical Technology (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Micromachines (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
本发明公开了一种人工类囊体微流控芯片及其制备方法，由两片微流控芯片通道上下键合而成，所述人工类囊体微流控芯片通道的上层结构内表面固定有光催化材料，所述人工类囊体微流控芯片通道的下层结构内表面固定有氧化还原酶，上下层结构表面固定材料互不接触、互不干扰，应用在高效光催化烟酰型辅酶再生方面。解决了现有光催化辅酶再生体系中光催化材料回收步骤复杂，氧化还原酶利用率低、稳定性差、不易回收，以及光催化材料与生物催化酶相容性差等缺点。
Description
发明领域
本发明属于生物化学技术领域，具体涉及一种人工类囊体微流控芯片及其制备方法与应用。
背景技术
目前有关人工类囊体的应用，有关其烟酰型辅酶再生与氧化还原酶反应，有的是两部分反应前后串联，有的是将氧化还原酶以游离酶形式加入到烟酰型辅酶再生悬浮系统中，这两种反应方式存在光催化材料回收步骤复杂，氧化还原酶利用率低、稳定性差、不易回收，以及光催化材料与生物催化酶相容性差等缺点。
发明内容
针对现有技术的不足，本发明提供了一种人工类囊体微流控芯片及其制备方法，应用在高效光催化烟酰型辅酶再生方面，解决了现有光催化辅酶再生体系中光催化材料回收步骤复杂，氧化还原酶利用率低、稳定性差、不易回收，以及光催化材料与生物催化酶相容性差等缺点。
本发明具体的技术方案是这样实现的：
一种人工类囊体微流控芯片，由两片微流控芯片通道上下键合而成，形成上层结构与下层结构构成的空腔，所述空腔上层结构的内表面涂布有光催化材料，所述空腔下层结构的内表面先加入3-氨丙基三乙氧基硅烷、后加入多巴胺进行化学改性，再在所述空腔下层结构的内表面注入谷氨酸脱氢酶溶液。
所述空腔的两端设置有进样口和出样口，即：所述进样口和出样口设置在上层结构，与所述空腔相连通。
所述光催化材料是采用涂布法涂布在所述空腔上层结构的内表面，即：在制作好的PDMS微流控芯片通道内由未聚合的PDMS粘附，PDMS受热固化后即将目标光催化材料固定在通道内。
所述光催化材料为g-C3N4量子点、mpg-C3N4或2D COF中的一种，优选为 2D COF。上述光催化材料均是按照现有的方法进行自行制备。
本发明所述人工类囊体微流控芯片是由两片微流控芯片通道上下键合而成，所述人工类囊体微流控芯片通道的上层结构内表面固定有光催化材料，所述人工类囊体微流控芯片通道的下层结构内表面固定有氧化还原酶，上下层结构分别固定、互不干扰。这里所述的氧化还原酶，指的是谷氨酸脱氢酶。
光反应过程中，所述人工类囊体微流控芯片通道的上层结构内表面固定的光催化材料吸收光能，对下层结构内表面固定的氧化还原酶层形成遮挡，实现烟酰型辅酶再生及氧化还原酶催化的同时，无需进行额外的避光步骤，这样氧化还原酶的蛋白结构不会被光催化材料表面的光生空穴破坏，进而实现：人工类囊体微流控芯片通道的上层结构光催化体系将烟酰型辅酶再生形成还原态烟酰型辅酶，还原态烟酰型辅酶扩散至下层结构与氧化还原酶反应，生成产物的同时，还原态烟酰型辅酶变为氧化态，氧化态烟酰型辅酶扩散回上层再次反应成为还原态，进而实现光催化的烟酰型辅酶再生及重复利用。
所述烟酰型辅酶是NADP+/NAD+或NADPH/NADH中的一种。
所述人工类囊体微流控芯片具有高比表面积、高扩散速率的优点，其烟酰型辅酶再生与氧化还原酶反应同时进行，可有效提高反应效率和烟酰型辅酶再生效率，可实现烟酰型辅酶高效利用及氧化还原酶高效催化，实现成本大幅降低。
所述人工类囊体微流控芯片的制备方法，包括以下步骤：
(1)将PDMS预聚物和PDMS固化剂按质量比10:1的比例配制，搅拌均匀，用真空泵除去气泡，制得混合好的PDMS混合液；
(2)通过软刻蚀技术制作SU-8模具，通过倒模法分别制成两片相同的微流控芯片；
(3)取一片步骤(2)得到的微流控芯片，将微流控芯片与平面玻璃板贴合密封，将3-氨丙基三乙氧基硅烷和聚多巴胺先后注入所述微流控芯片通道的内表面进行化学改性，再注入谷氨酸脱氢酶溶液，得到谷氨酸脱氢酶固定化微流控芯片；
(4)取另一片步骤(2)得到的微流控芯片，将光催化材料涂布在所述微流控芯片通道的内表面，再在所述微流控芯片通道两端打孔；
(5)将步骤(4)得到的微流控芯片作为上层结构，与步骤(5)得到的微流控芯片作为下层结构进行键合，即为人工类囊体微流控芯片。
步骤(1)所述PDMS预聚物和PDMS固化剂的型号：RTV615，来源： MomentivePerformance Materials，Waterford，NY，US。
步骤(3)将微流控芯片与平面玻璃板贴合密封，目的是为了形成闭合通道进行改性酶固定化。所述3-氨丙基三乙氧基硅烷与多巴胺发生反应，依此实现化学改性，先在通道内注满3-氨丙基三乙氧基硅烷孵育3～5小时，用1摩尔NaOH 溶液将3-氨丙基三乙氧基硅烷冲出后，再将通道注满多巴胺孵育8-10小时，即可完成化学改性。
步骤(3)所述谷氨酸脱氢酶溶液的浓度为1mg/ml-15mg/ml。
步骤(4)所述光催化材料为g-C3N4量子点、mpg-C3N4或2D COF中的一种，优选为2DCOF。
所述人工类囊体微流控芯片的应用，是在高效光催化烟酰型辅酶再生方面的应用。
本发明所制备的人工类囊体微流控芯片是一种基于微流控技术、光催化技术与酶固定化技术，模拟植物类囊体结构的烟酰型辅酶还原与氧化还原酶应用系统。与传统的人工类囊体反应系统相比，本发明所述人工类囊体微流控芯片，具有以下优点：①光催化剂固定在所述人工类囊体微流控芯片通道的上层结构的内表面，受光均匀，光利用率高，光催化材料重复利用，无需复杂的回收步骤；②氧化还原酶固定于所述人工类囊体微流控芯片通道的下层结构的内表面，酶活降低速度慢，易储存，反应结束无需从反应液内分离，简单高效；③烟酰型辅酶再生与氧化还原酶反应同时进行，所述人工类囊体微流控芯片比表面积高、扩散距离短、扩散效率高，可大幅提升烟酰型辅酶利用率及反应效率；④光催化材料与氧化还原酶分开固定，氧化还原酶的蛋白结构不会被光催化材料表面的光生空穴破坏，具备极高的光催-生物催化体系相容性。
本发明所制备的人工类囊体微流控芯片，应用在高效光催化烟酰型辅酶再生方面，具有光催化烟酰型辅酶再生利用充分、氧化还原酶利用率高、易回收、提高了光催化与生物催化相容性的优点。
附图说明
图1是所述人工类囊体微流控芯片的装配示意图；
图2是所述人工类囊体微流控芯片的结构示意图；
图3是烟酰型辅酶NADH再生速率图；
图4是烟酰型辅酶NADH再生动力学图；
图5是利用再生的NADH进行谷氨酸合成，12分钟处显示98％的α-酮戊二酸转化为谷氨酸。
图中1是上层结构，2是下层结构，3是空腔，4是进样口，5是出样口。
具体实施方式
本发明所述光催化材料为g-C3N4量子点、mpg-C3N4或2D COF中的一种，上述光催化材料均按照现有方法自行制备。
所述mpg-C3N4的合成方法：将5g的氰胺和12.5g的Ludox-HS 40硅胶悬浮液(固形比为1∶1)混合，直到氰胺完全溶解，使用在100℃的油浴除去水，用研钵和研杵研磨所得白色固体后，将其转移到坩埚中，并在空气下于2.3℃/min 的条件下4小时将其加热至550℃，并将样品保持在550℃再保持4个小时；所得黄色粉末用4M NH4HF2溶液处理并搅拌48小时，然后将分散体过滤，沉淀物用去离子水和乙醇彻底漂洗；过滤之后，将黄色粉末在真空(60℃)下干燥过夜。
所述g-C3N4量子点，采用超声剥离法制备：首先，以三聚氰胺为前驱体进行直接热聚合获得g-C3N4，然后依次通过酸剥离、水热、超声振荡等步骤逐步剥离制备出g-C3N4量子点；mpg-C3N4采用二氧化硅模板法制备，首先按固体质量比1:1混合氰胺与Ludox-HS 40胶态二氧化硅悬浮液，油浴除水，研磨后使其热聚合，用NH4HF2溶解二氧化硅模板，洗涤、干燥后制得。
所述2D COF的制备是按照文献Zhao Y,Liu H,Wu C,et al.Fully conjugatedtwo-dimensional sp2-carbon covalent organic frameworks as artificialphotosystem I with high efficiency[J].Angewandte Chemie InternationalEdition, 2019,58(16):5376-5381.中所公开的方法进行制备的。
实施例1
所述人工类囊体微流控芯片，由两片微流控芯片通道上下键合而成，形成上层结构1与下层结构2构成的空腔3，所述空腔3上层结构1的内表面涂布有 mpg-C3N4，所述空腔3下层结构2的内表面先加入3-氨丙基三乙氧基硅烷、后加入多巴胺进行化学改性，再在所述空腔3下层结构2的内表面注入浓度为 1mg/ml的谷氨酸脱氢酶溶液。
所述空腔3的两端设置有进样口4和出样口5。
所述人工类囊体微流控芯片的制备方法，包括以下步骤：
(1)将PDMS预聚物和固化剂按质量比10:1的比例配制，搅拌均匀，用真空泵除去气泡，制得混合好的PDMS混合液；
(2)通过软刻蚀技术制作SU-8模具，通过倒模法分别制成两片相同的微流控芯片；
(3)取一片步骤(2)得到的微流控芯片，将微流控芯片与平面玻璃板贴合密封，将3-氨丙基三乙氧基硅烷和多巴胺先后注入所述微流控芯片通道的内表面进行化学改性，再注入浓度为1mg/ml的谷氨酸脱氢酶溶液，得到谷氨酸脱氢酶固定化微流控芯片；
(4)取另一片步骤(2)得到的微流控芯片，将mpg-C3N4涂布在所述微流控芯片通道的内表面，再在所述微流控芯片通道两端打孔；
(5)将步骤(4)得到的微流控芯片作为上层结构，与步骤(5)得到的微流控芯片作为下层结构进行键合，即为人工类囊体微流控芯片。
所述人工类囊体微流控芯片的应用，在高效光催化烟酰型辅酶再生方面的应用。
实施例2
所述人工类囊体微流控芯片，由两片微流控芯片通道上下键合而成，形成上层结构1与下层结构2构成的空腔3，所述空腔3上层结构1的内表面涂布有 2D COF，所述空腔3下层结构2的内表面先加入3-氨丙基三乙氧基硅烷、后加入多巴胺进行化学改性，再在所述空腔3下层结构2的内表面注入浓度为8mg/ml 的谷氨酸脱氢酶溶液。
所述空腔3的两端设置有进样口4和出样口5。
所述人工类囊体微流控芯片的制备方法，包括以下步骤：
(1)将PDMS预聚物和固化剂按质量比10:1的比例配制，搅拌均匀，用真空泵除去气泡，制得混合好的PDMS混合液；
(2)通过软刻蚀技术制作SU-8模具，通过倒模法分别制成两片相同的微流控芯片；
(3)取一片步骤(2)得到的微流控芯片，将微流控芯片与平面玻璃板贴合密封，将3-氨丙基三乙氧基硅烷和多巴胺先后注入所述微流控芯片通道的内表面进行化学改性，再注入浓度为8mg/ml的谷氨酸脱氢酶溶液，得到谷氨酸脱氢酶固定化微流控芯片；
(4)取另一片步骤(2)得到的微流控芯片，将2D COF涂布在所述微流控芯片通道的内表面，再在所述微流控芯片通道两端打孔；
(5)将步骤(4)得到的微流控芯片作为上层结构，与步骤(5)得到的微流控芯片作为下层结构进行键合，即为人工类囊体微流控芯片。
所述人工类囊体微流控芯片的应用，在高效光催化烟酰型辅酶再生方面的应用。
实施例3
所述人工类囊体微流控芯片，由两片微流控芯片通道上下键合而成，形成上层结构1与下层结构2构成的空腔3，所述空腔3上层结构1的内表面涂布有 g-C3N4量子点，所述空腔3下层结构2的内表面先加入3-氨丙基三乙氧基硅烷、后加入多巴胺进行化学改性，再在所述空腔3下层结构2的内表面注入浓度为 15mg/ml的谷氨酸脱氢酶溶液。
所述空腔3的两端设置有进样口4和出样口5。
所述人工类囊体微流控芯片的制备方法，包括以下步骤：
(1)将PDMS预聚物和固化剂按质量比10:1的比例配制，搅拌均匀，用真空泵除去气泡，制得混合好的PDMS混合液；
(2)通过软刻蚀技术制作SU-8模具，通过倒模法分别制成两片相同的微流控芯片；
(3)取一片步骤(2)得到的微流控芯片，将微流控芯片与平面玻璃板贴合密封，将3-氨丙基三乙氧基硅烷和多巴胺先后注入所述微流控芯片通道的内表面进行化学改性，再注入浓度为15mg/ml的谷氨酸脱氢酶溶液，得到谷氨酸脱氢酶固定化微流控芯片；
(4)取另一片步骤(2)得到的微流控芯片，将g-C3N4量子点涂布在所述微流控芯片通道的内表面，再在所述微流控芯片通道两端打孔；
(5)将步骤(4)得到的微流控芯片作为上层结构，与步骤(5)得到的微流控芯片作为下层结构进行键合，即为人工类囊体微流控芯片。
所述人工类囊体微流控芯片的应用，在高效光催化烟酰型辅酶再生方面的应用。
试验例
将实施例所制备的人工类囊体微流控芯片进行相关静态实验、动态实验和反应器重复性试验进行效果验证：
(1)静态实验
将由二氯(五甲基环戊二烯基)合铑(III)(0.2～1.5mM)，NAD+(1～2mM)，α-酮戊二酸(0.5～2mM)，硫酸铵(50～100mM)，磷酸缓冲液(50～100mM)， TEOA(5％～20％w/v)组成的反应溶液注满制备完成的人工类囊体微流控芯片中，堵住进样口及出样口，在模拟太阳光(光源固定为300W的氙灯)下进行烟酰型辅酶再生反应；
(2)动态实验
使用精密注射泵(型号：LSP02-2A，厂家：LongerPump)以不同流速向光催化微流控反应器中灌注由二氯(五甲基环戊二烯基)合铑(III)(0.2～1.5mM)， NAD+(1～2mM)，α-酮戊二酸(0.5～2mM)，硫酸铵(50～100mM)，磷酸缓冲液(50～100mM)，TEOA(5％～20％w/v)组成的反应液，流速设计范围为5 μL/min至50μL/min，通过控制流速实现对光照时间的控制在模拟太阳光(光源固定为300W的氙灯)下进行反应，并在出样口收集、检测反应完成的反应液，探索不同流速对NADH再生速率的影响，获得最优光照时间；
(3)人工类囊体微流控芯片产率测试
利用2D COF进行人工光合作用烟酰型辅酶再生及L-谷氨酸合成：图3烟酰型辅酶NADH再生速率图显示，340nm处为NADH的特征吸收峰；图4NADH 再生动力学图显示：在光照10分钟内，随着光照时间增加，反应效率不断提升，最高可达90.35％；图5利用再生的NADH进行谷氨酸合成，12分钟处显示98％的α-酮戊二酸转化为谷氨酸。
Claims (9)
1.一种人工类囊体微流控芯片，其特征在于：由两片微流控芯片通道上下键合而成，形成上层结构(1)与下层结构(2)构成的空腔(3)，所述空腔(3)上层结构(1)的内表面涂布有光催化材料，所述空腔(3)下层结构(2)的内表面先加入3-氨丙基三乙氧基硅烷、后加入多巴胺进行化学改性，再在所述空腔(3)下层结构(2)的内表面注入谷氨酸脱氢酶溶液。
2.根据权利要求1所述人工类囊体微流控芯片，其特征在于：所述空腔(3)的两端设置有进样口(4)和出样口(5)。
3.根据权利要求1或2所述人工类囊体微流控芯片，其特征在于：所述光催化材料为g-C3N4量子点、mpg-C3N4或2D COF中的一种。
4.根据权利要求3所述人工类囊体微流控芯片，其特征在于：所述光催化材料为2DCOF。
5.制备如权利要求1或2所述人工类囊体微流控芯片的方法，其特征在于：包括以下步骤：
(1)将PDMS预聚物和固化剂按质量比10:1的比例配制，搅拌均匀，用真空泵除去气泡，制得混合好的PDMS混合液；
(2)通过软刻蚀技术制作SU-8模具，通过倒模法分别制成两片相同的微流控芯片；
(3)取一片步骤(2)得到的微流控芯片，将微流控芯片与平面玻璃板贴合密封，将3-氨丙基三乙氧基硅烷和多巴胺先后注入所述微流控芯片通道的内表面进行化学改性，再注入谷氨酸脱氢酶溶液，得到谷氨酸脱氢酶固定化微流控芯片；
(4)取另一片步骤(2)得到的微流控芯片，将光催化材料涂布在所述微流控芯片通道的内表面，再在所述微流控芯片通道两端打孔；
(5)将步骤(4)得到的微流控芯片作为上层结构，与步骤(5)得到的微流控芯片作为下层结构进行键合，即为人工类囊体微流控芯片。
6.根据权利要求5所述人工类囊体微流控芯片的制备方法，其特征在于：步骤(3)所述谷氨酸脱氢酶溶液的浓度为1mg/ml-15mg/ml。
7.根据权利要求5或6所述人工类囊体微流控芯片的制备方法，其特征在于：步骤(4)所述光催化材料为g-C3N4量子点、mpg-C3N4或2D COF中的一种。
8.根据权利要求7所述人工类囊体微流控芯片的制备方法，其特征在于：步骤(4)所述光催化材料为2D COF。
9.如权利要求1-4任一所述人工类囊体微流控芯片的应用，其特征在于：在高效光催化烟酰型辅酶再生方面的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110293147.4A CN113058667B (zh) | 2021-03-18 | 2021-03-18 | 一种人工类囊体微流控芯片及其制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110293147.4A CN113058667B (zh) | 2021-03-18 | 2021-03-18 | 一种人工类囊体微流控芯片及其制备方法与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113058667A true CN113058667A (zh) | 2021-07-02 |
| CN113058667B CN113058667B (zh) | 2022-05-17 |
Family
ID=76562223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110293147.4A Active CN113058667B (zh) | 2021-03-18 | 2021-03-18 | 一种人工类囊体微流控芯片及其制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113058667B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162278A (en) * | 1999-05-12 | 2000-12-19 | UT-- Battelle, LLC | Photobiomolecular deposition of metallic particles and films |
| CN107376799A (zh) * | 2017-09-15 | 2017-11-24 | 重庆大学 | 一种高效的光催化反应器 |
| US20200102543A1 (en) * | 2017-06-13 | 2020-04-02 | Dai Nippon Printing Co., Ltd. | Gut organoid and method for producing the same |
| CN111346575A (zh) * | 2020-03-31 | 2020-06-30 | 齐鲁工业大学 | 催化材料固定区域可控的毛细管微流控反应器及制备方法 |
-
2021
- 2021-03-18 CN CN202110293147.4A patent/CN113058667B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162278A (en) * | 1999-05-12 | 2000-12-19 | UT-- Battelle, LLC | Photobiomolecular deposition of metallic particles and films |
| US20200102543A1 (en) * | 2017-06-13 | 2020-04-02 | Dai Nippon Printing Co., Ltd. | Gut organoid and method for producing the same |
| CN107376799A (zh) * | 2017-09-15 | 2017-11-24 | 重庆大学 | 一种高效的光催化反应器 |
| CN111346575A (zh) * | 2020-03-31 | 2020-06-30 | 齐鲁工业大学 | 催化材料固定区域可控的毛细管微流控反应器及制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| XIAOWEN HUANG: "Microfluidic chip-based one-step fabrication of an artificial photosystem I for photocatalytic cofactor", 《RSC ADVANCES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113058667B (zh) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Bio-inspired NADH regeneration by carbon nitride photocatalysis using diatom templates | |
| Zhou et al. | Construction of multi-enzyme cascade biomimetic carbon sequestration system based on photocatalytic coenzyme NADH regeneration | |
| CN106397797B (zh) | 一种金-MOFs-聚合物复合膜及其制备方法与应用 | |
| Chai et al. | Biocatalytic micromixer coated with enzyme-MOF thin film for CO2 conversion to formic acid | |
| CN108816234B (zh) | 一种基于ldh固定过渡金属mof的衍生物催化剂的制备方法及其应用 | |
| CN111266068B (zh) | 一种接枝负载催化剂的纳米结构微通道基底的微反应器及其制备方法 | |
| CN104923276B (zh) | 一种石墨型氮化碳复合铁酸镍磁性光催化材料的制备方法 | |
| CN107349961A (zh) | 一种NH2‑UIO‑66@TpPa‑1复合材料的制备及光解水制氢 | |
| CN107008259B (zh) | 核壳结构纳米金团簇-二氧化钛复合型催化剂 | |
| CN109201120A (zh) | 可见光催化产氢的中空TiO2@ZIF-8异质结催化剂及其制备方法 | |
| CN114515581B (zh) | 掺杂型CdS光催化剂及其在催化转化CO2中的应用 | |
| CN108607593A (zh) | 硫化镉纳米粒子修饰的五氧化二铌纳米棒/氮掺杂石墨烯复合光催化剂与应用 | |
| CN106807404B (zh) | 一种非贵金属基碳包覆硫化镍光催化剂的制备方法及其应用 | |
| Chen et al. | Orderly cascade of immobilized-enzyme catalysis and photocatalysis for continuous-microflow production of 2-phenylbenzothiazole | |
| CN113058667B (zh) | 一种人工类囊体微流控芯片及其制备方法与应用 | |
| CN115970765B (zh) | 具有3d三相界面的仿生可漂浮光催化材料、制备方法及其在光催化氮还原合成氨中的应用 | |
| CN113981478A (zh) | 介孔材料固定化酶进行生物电催化二氧化碳还原的方法及应用 | |
| Singh et al. | Polystyrene-based eosin-Y as a photocatalyst for solar light-mediated NADH/NADPH regeneration and organic transformations | |
| Wang et al. | An easy fabricated biomimetic leaf microreactor for photocatalytic nicotinamide adenine dinucleotide (NADH) regeneration | |
| CN107754857B (zh) | 一种还原co2光催化剂及其制备方法与应用 | |
| CN108786924A (zh) | 一种Ni(OH)2/TpPa-2材料的制备方法 | |
| Bai et al. | Advances in photo-enzymatic-coupling catalysis system | |
| CN211988550U (zh) | 一种微通道内接枝纳米结构的光催化装置 | |
| Zhou et al. | In-CdS@ ZIF-8&FDH photo-enzyme nanosystem with high NADH regeneration ability via indium doping for enhanced CO2 reduction to formic acid | |
| CN110124746A (zh) | 一种磷化镍/TpPa-2复合材料的制备及光解水制氢 |
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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Xiaowen Inventor after: Liu Yang Inventor after: Lin Huichao Inventor before: Liu Yang Inventor before: Huang Xiaowen Inventor before: Lin Huichao |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 3501, Daxue Road, Changqing District, Jinan City, Shandong Province Patentee after: Qilu University of Technology (Shandong Academy of Sciences) Country or region after: China Patentee after: Shandong Youjian Biotechnology Co.,Ltd. Address before: No. 3501, Daxue Road, Changqing District, Jinan City, Shandong Province Patentee before: Qilu University of Technology Country or region before: China Patentee before: Shandong Youjian Biotechnology Co.,Ltd. |