CN110773009A - Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane - Google Patents
Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane Download PDFInfo
- Publication number
- CN110773009A CN110773009A CN201911190685.XA CN201911190685A CN110773009A CN 110773009 A CN110773009 A CN 110773009A CN 201911190685 A CN201911190685 A CN 201911190685A CN 110773009 A CN110773009 A CN 110773009A
- Authority
- CN
- China
- Prior art keywords
- zinc
- alginate
- phosphate
- hydrogel
- calcium
- 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
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 104
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 104
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229940072056 alginate Drugs 0.000 title claims abstract description 103
- 239000000017 hydrogel Substances 0.000 title claims abstract description 88
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title claims abstract description 66
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 238000001914 filtration Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 70
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 26
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000661 sodium alginate Substances 0.000 claims abstract description 24
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 24
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 15
- 239000000648 calcium alginate Substances 0.000 claims abstract description 14
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 14
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 14
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 6
- 238000004042 decolorization Methods 0.000 claims abstract description 4
- 238000010612 desalination reaction Methods 0.000 claims abstract description 4
- 238000004043 dyeing Methods 0.000 claims abstract description 4
- 229920001184 polypeptide Polymers 0.000 claims abstract description 4
- 238000007639 printing Methods 0.000 claims abstract description 4
- 102000004196 processed proteins & peptides Human genes 0.000 claims abstract description 4
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 4
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 4
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 24
- 238000005345 coagulation Methods 0.000 claims description 14
- 230000015271 coagulation Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 9
- 241000894006 Bacteria Species 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000002504 physiological saline solution Substances 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 3
- 239000004227 calcium gluconate Substances 0.000 claims description 3
- 235000013927 calcium gluconate Nutrition 0.000 claims description 3
- 229960004494 calcium gluconate Drugs 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002522 swelling effect Effects 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241000191963 Staphylococcus epidermidis Species 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003501 co-culture Methods 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
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229910001656 zinc mineral Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/74—Natural macromolecular material or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Abstract
The invention discloses a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate. Firstly, fully mixing and dissolving soluble phosphate and sodium alginate to obtain a membrane casting solution. The casting solution is scraped into a film and is soaked in a soluble zinc salt aqueous solution for full crosslinking, and zinc phosphate is generated in situ in the hydrogel while the zinc alginate hydrogel is generated. And then soaking the obtained zinc alginate hydrogel membrane containing zinc phosphate in an aqueous solution of soluble calcium salt, and capturing partial zinc ions in the zinc alginate by the calcium ions to generate calcium alginate, thereby obtaining the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane. The phosphate generated in situ in the hydrogel improves the mechanical property of the alginate hydrogel, reduces the swelling property of the hydrogel, and the zinc phosphate endows the alginate hydrogel with good antibacterial property. The filter membrane has good application prospect in the fields of dye desalination, printing and dyeing wastewater decolorization, protein and polypeptide purification and the like.
Description
Technical Field
The invention relates to a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, belonging to the field of functional materials and membrane separation.
The invention relates to the technical fields of filtering membranes, hydrogels, antibacterium and the like. In particular to a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate.
Background
The membrane separation technology is an environment-friendly new technology, does not produce secondary pollution, has low energy consumption and simple operation compared with the traditional wastewater treatment method, and is one of the most promising water treatment technologies at present. The traditional membrane is usually made of inorganic materials, organic high molecular materials or inorganic-organic composite materials, and the structure of the traditional membrane is divided into a plurality of types; different materials and structures determine the direction of application and the degree of separation of the membrane, and thus correspond to different applications. The polymer membrane has the advantages of small size, low energy consumption, simple preparation, low price and the like, but has certain disadvantages, such as poor organic solvent resistance, easy membrane pollution generation, easy bacteria breeding and the like.
The polymer gel is a multi-element system consisting of a polymer three-dimensional network and a solvent, and the hydrogel has good hydrophilicity because the hydrogel contains more than 80% of water. Sodium alginate is a natural high molecular substance which can be extracted from kelp or brown algae, has wide sources and low price, and is widely applied to the fields of food, biological medicine, wastewater treatment and the like at present. Sodium alginate and calcium ions can form hydrogel through ionic crosslinking. Zhao Kong Yin, etc. have prepared a series of calcium alginate-based hydrogel filtration membranes [ patent of invention ZL201310424398.7, ZL201310424399.1, ZL201310424397.2 ], these calcium alginate-based filtration membranes have good anti-pollution performance, but have the disadvantages of poor mechanical properties, low mechanical strength and easy degradation by bacteria.
Malaguerski I, et al prepared a metallic Zn sodium alginate based nanocomposite by a simple process, impregnating carbonate and phosphate mineral phases [ mater.Lett, 2018, 212, 32-36 ]. The mineralized samples exhibited different morphology and properties compared to the unmineralized samples. Bacteriostatic tests on escherichia coli, staphylococcus aureus and candida albicans show that the mineralized sample has higher removal efficiency on microorganisms than an unmineralized sample. The metal zinc mineralized alginate can be used as an antibacterial material with low price and easy production. Meanwhile, Malagurski I et al also studied the synthesis and antibacterial properties of zinc mineralized sodium alginate nanocomposites. The novel bioactive antibacterial material is prepared by adopting sodium alginate-mediated zinc mineral phase biomineralization. The synthesis process is simple and low in cost, and prepares two different zinc alginate mineralized nanometer composite materials of zinc carbonate/zinc alginate and zinc phosphate/zinc alginate. Aiming at the antibacterial property research of sodium alginate containing zinc ions, turlybekulya et al researches the biocompatibility and antibacterial property of a composite material by using analytically pure sodium alginate-hydroxyapatite-sodium alginate dual-phase zinc oxide and hydroxyapatite-zinc oxide as main raw materials and adopting orthogonal experimental design [ mater.sci.eng, 2019, 104, 109965 ]. The antibacterial activity evaluation is carried out on gram-negative bacteria (escherichia coli and pseudomonas aeruginosa) and gram-positive bacteria (staphylococcus aureus and staphylococcus epidermidis) by adopting a co-culture method and an improved agar diffusion method. Biocompatibility experiments and cytotoxicity evaluations were performed with mouse fibroblasts. The embedding process of zinc ions in hydroxyapatite and sodium alginate matrixes is illustrated, and the influence of the zinc ions on the performance of the bionic composite material is discussed in detail. Multiple studies show that zinc can effectively inhibit the growth and development of bacteria and yeasts. Zinc plays an important role in the development of novel antibacterial agents, and zinc-doped hydroxyapatite is further applied to biomedicine. In this respect, the phase of zinc oxide, as well as the calcium replacement process of zinc in calcium apatites and alginates, should be well explored.
The invention discloses a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate. Firstly, fully mixing and dissolving soluble phosphate and sodium alginate to obtain a membrane casting solution. The casting solution is scraped into a film and is soaked in a soluble zinc salt aqueous solution for full crosslinking, and zinc phosphate is generated in situ in the hydrogel while the zinc alginate hydrogel is generated. And then soaking the obtained zinc alginate hydrogel membrane containing zinc phosphate in an aqueous solution of soluble calcium salt, and capturing partial zinc ions in the zinc alginate by the calcium ions to generate calcium alginate, thereby obtaining the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane. The phosphate generated in situ in the hydrogel improves the mechanical property of the alginate hydrogel, reduces the swelling property of the hydrogel, and the zinc phosphate endows the alginate hydrogel with good antibacterial property. The filter membrane has good application prospect in the fields of dye desalination, printing and dyeing wastewater decolorization, protein and polypeptide purification and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, and the calcium alginate hydrogel filtering membrane has low strength and is easy to degrade by bacteria.
The invention provides a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, and solves the problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, is low in strength of a calcium alginate hydrogel filtering membrane, is easy to degrade by bacteria and the like.
The invention provides a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, which is characterized by comprising the following steps:
a) preparing a mixture water solution of soluble phosphate with the mass percentage concentration of 0.1-20% and sodium alginate with the mass percentage concentration of 0.2-8%, standing and defoaming to obtain a membrane casting solution;
b) preparing a soluble zinc salt water solution with the mass percentage concentration of 0.2-20% as a first coagulating bath; preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a second coagulating bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20-1500 mu m, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 5-240min to obtain a zinc alginate/zinc phosphate hydrogel film; when the soluble zinc salt reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with soluble phosphate, the zinc phosphate salt and the alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 20-80% compared with the tensile strength of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 20-65% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 5-240min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the alginate hydrogel antibacterial filtering membrane containing zinc phosphate is obtained.
The soluble phosphate is any one or a mixture of two or more of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate and trisodium phosphate; the soluble calcium salt is any one or mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate; the soluble zinc salt is any one or a mixture of two or more of zinc chloride, zinc nitrate, zinc sulfate and zinc acetate.
In the invention, zinc phosphate and zinc ions of cross-linked sodium alginate endow alginate hydrogel with good antibacterial performance, so that the calcium alginate hydrogel filtering membrane is prevented from being degraded by bacteria in the using process, has good pollution resistance, and has good application prospect in dye desalination, emulsion oil separation, printing and dyeing wastewater decolorization and protein and polypeptide purification.
Detailed Description
Specific examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1.
a) Preparing a mixture water solution of diammonium phosphate with the mass percentage concentration of 0.1% and sodium alginate with the mass percentage concentration of 0.2%, and standing and defoaming to obtain a membrane casting solution;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 0.2 percent as a first coagulating bath; preparing a calcium chloride aqueous solution with the mass percentage concentration of 0.2 percent as a second coagulation bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20 microns, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 5min to obtain a zinc alginate/zinc phosphate hydrogel film; when zinc chloride reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with diammonium hydrogen phosphate, zinc phosphate salt and alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 20% compared with that of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 65% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 5min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane is obtained.
Example 2.
a) Preparing a mixture aqueous solution of 20 mass percent of disodium hydrogen phosphate and 8 mass percent of sodium alginate, and standing and defoaming to obtain a membrane casting solution;
b) preparing a zinc nitrate aqueous solution with the mass percentage concentration of 20% as a first coagulating bath; preparing a calcium nitrate water solution with the mass percentage concentration of 20% as a second coagulating bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 1500 mu m, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 240min to obtain a zinc alginate/zinc phosphate hydrogel film; when zinc nitrate reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with disodium hydrogen phosphate, zinc phosphate salt and alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 80% compared with that of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 20% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 240min, wherein the binding capacity of calcium ions and alginate is stronger than that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the alginate hydrogel antibacterial filtering membrane containing zinc phosphate is obtained.
Example 3.
a) Preparing a mixture aqueous solution of dipotassium phosphate with the mass percentage concentration of 16% and sodium alginate with the mass percentage concentration of 6%, standing and defoaming to obtain a membrane casting solution;
b) preparing a zinc sulfate aqueous solution with the mass percentage concentration of 16% as a first coagulating bath; preparing a calcium dihydrogen phosphate water solution with the mass percentage concentration of 16 percent as a second coagulating bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 1000 microns, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 210min to obtain a zinc alginate/zinc phosphate hydrogel film; when zinc sulfate reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with dipotassium hydrogen phosphate, zinc phosphate salt and alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 40% compared with that of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 45% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 210min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane is obtained.
Example 4.
a) Preparing a mixture aqueous solution of tripotassium phosphate with the mass percentage concentration of 10% and sodium alginate with the mass percentage concentration of 3%, standing and defoaming to obtain a membrane casting solution;
b) preparing a zinc acetate water solution with the mass percentage concentration of 10% as a first coagulating bath; preparing a calcium gluconate aqueous solution with the mass percentage concentration of 3% as a second coagulation bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 800 microns, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 100min to obtain a zinc alginate/zinc phosphate hydrogel film; when zinc acetate reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with tripotassium phosphate, zinc phosphate salt and alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 75% compared with that of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 35% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 100min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane is obtained.
Claims (5)
1. A preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate is characterized by comprising the following steps:
a) preparing a mixture water solution of soluble phosphate with the mass percentage concentration of 0.1-20% and sodium alginate with the mass percentage concentration of 0.2-8%, standing and defoaming to obtain a membrane casting solution;
b) preparing a soluble zinc salt water solution with the mass percentage concentration of 0.2-20% as a first coagulating bath; preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a second coagulating bath;
c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with zinc wires with the diameter of 20-1500 mu m, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 5-240min to obtain a zinc alginate/zinc phosphate hydrogel film; when the soluble zinc salt reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with soluble phosphate, the zinc phosphate salt and the alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 20-80% compared with the tensile strength of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 20-65% of that of the zinc alginate;
d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 5-240min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the alginate hydrogel antibacterial filtering membrane containing zinc phosphate is obtained.
2. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, characterized in that the soluble phosphate is any one or a mixture of two or more of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate and trisodium phosphate.
3. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, wherein the soluble calcium salt is any one or a mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate.
4. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, characterized in that the soluble zinc salt is any one or a mixture of two or more of zinc chloride, zinc nitrate, zinc sulfate and zinc acetate.
5. The preparation method of the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane is characterized in that zinc ions of zinc phosphate and cross-linked sodium alginate endow the alginate hydrogel with good antibacterial performance, the calcium alginate hydrogel filtering membrane is prevented from being degraded by bacteria in the using process, the filtering membrane has good pollution resistance, and the filtering membrane has good application prospects in dye desalination, emulsion oil separation, printing and dyeing wastewater decolorization and protein and polypeptide purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911190685.XA CN110773009B (en) | 2019-11-29 | 2019-11-29 | Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911190685.XA CN110773009B (en) | 2019-11-29 | 2019-11-29 | Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110773009A true CN110773009A (en) | 2020-02-11 |
| CN110773009B CN110773009B (en) | 2021-11-09 |
Family
ID=69393064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911190685.XA Active CN110773009B (en) | 2019-11-29 | 2019-11-29 | Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110773009B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112221350A (en) * | 2020-09-25 | 2021-01-15 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on zinc hydroxide nanowires |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808313A (en) * | 1985-01-08 | 1989-02-28 | Agency Of Industrial Science And Technology | Liquid separation membrane for pervaporation |
| CN103357062A (en) * | 2012-03-26 | 2013-10-23 | 约泰实业股份有限公司 | Fibrous hydrogel and preparation method thereof |
| CN103446898A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN106994133A (en) * | 2016-01-25 | 2017-08-01 | 吉林省莱沃医疗科技有限公司 | Calcium zinc ion is combined antibacterial alginate slow-release material and preparation method thereof |
| CN109046046A (en) * | 2018-08-24 | 2018-12-21 | 西安建筑科技大学 | A kind of preparation method of nano material/Quorum quenching enzymes hydrogel nanofiltration membrane |
| CN110433336A (en) * | 2019-08-22 | 2019-11-12 | 暨南大学 | A kind of pre- mineralising natural polysaccharide based aquagel and the preparation method and application thereof |
-
2019
- 2019-11-29 CN CN201911190685.XA patent/CN110773009B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808313A (en) * | 1985-01-08 | 1989-02-28 | Agency Of Industrial Science And Technology | Liquid separation membrane for pervaporation |
| CN103357062A (en) * | 2012-03-26 | 2013-10-23 | 约泰实业股份有限公司 | Fibrous hydrogel and preparation method thereof |
| CN103446898A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN106994133A (en) * | 2016-01-25 | 2017-08-01 | 吉林省莱沃医疗科技有限公司 | Calcium zinc ion is combined antibacterial alginate slow-release material and preparation method thereof |
| CN109046046A (en) * | 2018-08-24 | 2018-12-21 | 西安建筑科技大学 | A kind of preparation method of nano material/Quorum quenching enzymes hydrogel nanofiltration membrane |
| CN110433336A (en) * | 2019-08-22 | 2019-11-12 | 暨南大学 | A kind of pre- mineralising natural polysaccharide based aquagel and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SIDI LI等: "Preparation of tricalcium phosphate–calcium alginate composite flat sheet membranes and their application for protein release", 《POLYMER COMPOSITES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112221350A (en) * | 2020-09-25 | 2021-01-15 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on zinc hydroxide nanowires |
| CN112221350B (en) * | 2020-09-25 | 2022-04-19 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on zinc hydroxide nanowires |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110773009B (en) | 2021-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110743400B (en) | Preparation method of copper ion-doped alginate hydrogel antibacterial filtering membrane | |
| CN110960992B (en) | Preparation method of silver nanoparticle-containing calcium alginate antibacterial filtering membrane | |
| Varadavenkatesan et al. | Synthesis, biological and environmental applications of hydroxyapatite and its composites with organic and inorganic coatings | |
| CN110743397B (en) | Preparation method of silver phosphate-containing calcium alginate antibacterial hydrogel filtering membrane | |
| CN104548969A (en) | Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions | |
| Kumar et al. | Preparation and evaluation of heavy metal rejection properties of polysulfone/chitosan, polysulfone/N-succinyl chitosan and polysulfone/N-propylphosphonyl chitosan blend ultrafiltration membranes | |
| CN102049204B (en) | Metal ion-carried nerchinskite nano tube/polyether sulfone hybridized antibacterial membrane and preparation method thereof | |
| CN101053782B (en) | Antibiotic cellulose acetate nanofiltration membrane and its preparation method | |
| CN110773008B (en) | Preparation method of copper phosphate-containing alginate hydrogel antibacterial filtering membrane | |
| CN110773007B (en) | Calcium alginate hydrogel filtering membrane containing black phosphorus/graphene oxide and preparation method thereof | |
| Mao et al. | Impact of various coagulation technologies on membrane fouling in coagulation/ultrafiltration process | |
| CN110773006B (en) | Preparation method of hydrogel antibacterial filtering membrane containing copper oxide/cuprous oxide/carbon nano tube | |
| CN110773009B (en) | Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane | |
| CN107321333A (en) | A kind of preparation method for the hydrogel microsphere for adsorbing dye ions | |
| CN103663637A (en) | Complex bleaching flocculating agent used for metal plating wastewater and use method of complex bleaching flocculating agent | |
| CN102553466A (en) | Antimicrobial polysulphone flat ultrafiltration membrane and preparation method thereof | |
| Liu et al. | Silver nanoparticle-incorporated porous renewable film as low-cost bactericidal and antifouling filter for point-of-use water disinfection | |
| CN106178994A (en) | A kind of preparation method of antibacterial NF membrane | |
| EP4257556A2 (en) | Particles with biozidal coating | |
| JP2006305411A (en) | Eutrophic artificial seawater, and method for producing the same | |
| CN116603108A (en) | Nanometer wool protein/hydroxyapatite composite bionic bone material and preparation process thereof | |
| CN107138051B (en) | The method that one step reaction in-situ prepares antibiotic cellulose acetate reverse osmosis membrane | |
| CN106378011A (en) | Adsorption hyperfiltration membrane containing sodium polystyrenesulfonate and preparation method | |
| CN105112967A (en) | Preparation method of conductive coating layer having bone induction and antibacterial performances | |
| CN110773010A (en) | Preparation method of black phosphorus/copper ion-containing calcium alginate hydrogel antibacterial filtering membrane |
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 |
Effective date of registration: 20240116 Address after: 712000 Factory Building 5, South Zone 1, Hongshengxing Aviation Technology Industrial Park, Dunhua Road, Airport New City, Xixian New Area, Xianyang City, Shaanxi Province Patentee after: Xi'an Meinan Biotechnology Co.,Ltd. Address before: 300387 School of materials science and engineering, 399 West Pennsylvania Road, Xiqing, Tianjin Patentee before: TIANJIN POLYTECHNIC University |
|
| TR01 | Transfer of patent right |