CN105498559A - Composite membrane based on functional protein - Google Patents
Composite membrane based on functional protein Download PDFInfo
- Publication number
- CN105498559A CN105498559A CN201511008292.4A CN201511008292A CN105498559A CN 105498559 A CN105498559 A CN 105498559A CN 201511008292 A CN201511008292 A CN 201511008292A CN 105498559 A CN105498559 A CN 105498559A
- Authority
- CN
- China
- Prior art keywords
- functional protein
- aquaporin
- composite membrane
- active layer
- solution
- 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
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- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 71
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 29
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 49
- 239000010410 layer Substances 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 26
- 102000010637 Aquaporins Human genes 0.000 claims description 22
- 108010063290 Aquaporins Proteins 0.000 claims description 22
- 229940021013 electrolyte solution Drugs 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 229920000447 polyanionic polymer Polymers 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 11
- -1 amino, carboxyl Chemical group 0.000 claims description 8
- 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 description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 108090001004 Aquaporin 1 Proteins 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 108010036221 Aquaporin 2 Proteins 0.000 claims description 4
- 108090000991 Aquaporin 3 Proteins 0.000 claims description 4
- 108050006914 Aquaporin 9 Proteins 0.000 claims description 4
- 102100034414 Aquaporin-2 Human genes 0.000 claims description 4
- 102100037332 Aquaporin-3 Human genes 0.000 claims description 4
- 102100029464 Aquaporin-9 Human genes 0.000 claims description 4
- 101000655016 Arabidopsis thaliana Aquaporin TIP1-1 Proteins 0.000 claims description 4
- 102000014914 Carrier Proteins Human genes 0.000 claims description 4
- 108010078791 Carrier Proteins Proteins 0.000 claims description 4
- 101710128223 Chloride channel protein Proteins 0.000 claims description 4
- 102000004257 Potassium Channel Human genes 0.000 claims description 4
- 102000018674 Sodium Channels Human genes 0.000 claims description 4
- 108010052164 Sodium Channels Proteins 0.000 claims description 4
- 108010067973 Valinomycin Proteins 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 102000004891 aquaporin 8 Human genes 0.000 claims description 4
- 108090001000 aquaporin 8 Proteins 0.000 claims description 4
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 108020001213 potassium channel Proteins 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 claims description 4
- VVPXCQJEIWWMEH-UHFFFAOYSA-N 2-(2,5-dioxopyrrolidin-1-yl)pentanedioic acid Chemical class OC(=O)CCC(C(O)=O)N1C(=O)CCC1=O VVPXCQJEIWWMEH-UHFFFAOYSA-N 0.000 claims description 3
- NVWKYNBWYYJZTK-UHFFFAOYSA-N 8-(2,5-dioxopyrrolidin-1-yl)oxy-8-oxooctanoic acid Chemical class OC(=O)CCCCCCC(=O)ON1C(=O)CCC1=O NVWKYNBWYYJZTK-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 201000010099 disease Diseases 0.000 claims description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
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- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 4
- 102100023771 Aquaporin-1 Human genes 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 38
- 229960003638 dopamine Drugs 0.000 description 19
- 210000004379 membrane Anatomy 0.000 description 18
- 108050005714 Aquaporin Z Proteins 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003094 microcapsule Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000003904 phospholipids Chemical class 0.000 description 5
- 102000004888 Aquaporin 1 Human genes 0.000 description 4
- 210000000170 cell membrane Anatomy 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 238000001814 protein method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/74—Natural macromolecular material or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- D06M13/123—Polyaldehydes; Polyketones
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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- 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
- C08J2327/00—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 halogen; Derivatives of such polymers
- C08J2327/02—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 halogen; Derivatives of such polymers not modified by chemical after-treatment
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- 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
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a composite membrane based on a functional protein and a preparation method thereof. The composite membrane consists of a polyelectrolyte active layer on which the functional protein is embedded, and a supporting layer, wherein the functional protein is used as a functional unit and is directly embedded into a formed network structure in the process of assembling layer by layer to prepare the polyelectrolyte active layer, and by cross-linking and curing, combination firmness of the functional protein in the active layer is improved. The preparation method is simple in operation process, and embedding content of the functional protein in the composite membrane is improved. The functional protein composite membrane has a wide application prospect in the fields of water treatment and membrane separation.
Description
Technical field
The present invention relates to functional protein composite membrane technology field, being specifically related to a kind of composite membrane by forming containing the polyelectrolyte active layer of functional protein and preparation method, can be used for the fields such as desalinization, sewage disposal, Dye Removal, food processing, biological medicine and disease treatment.
Background technology
There is a serious shortage in the supply for freshwater resources, energy breach expands rapidly and environmental pollution is on the rise is the important bottleneck restricting human civilization health and sustainable development now.Membrane separation technique, because of advantages such as it is efficient, energy-saving and environmental protection, is subject to extensive use in the field such as sewage disposal, desalinization.But diffusion barrier is in preparations and applicatio process at present, there is " trade-off " effect between its flux and rejection, the flux namely improving diffusion barrier can reduce the separation accuracy of film, and the rejection improving film can reduce the flux of film.Therefore, " trade-off " effect that the diffusion barrier that how to break traditions exists, improves flux and the rejection of film simultaneously, and preparation high-performance diffusion barrier becomes the advanced subject in current diffusion barrier field.
At the nature of mystery, the cell membrane forming life entity basic functional units provides valuable enlightenment to the diffusion barrier obtaining high osmosis and high selectivity.20th century the mid-80, American scientist Peter A Gelei has found cell membrane aquaporin albumen, having verified water with high flux and high selectivity mode permeate through cell membranes is not simple free diffusing process, but completed by the class functional protein on cell membrane.Specifically, the hydrone quantity that aquaporin AQP1 molecule can transmit each second can up to 3,000,000,000 (about 10
14cm
3/ s), can stop that the component such as other nearly all Small molecular and ion (comprises proton H simultaneously
+).This is found to be the high water flux diffusion barrier of preparation and provides new approaches.2007, aquaporin AqpZ is embedded block copolymer micro-capsule by the people such as Switzerland scientist MeierW. and American scientist KumarM. first, the Water permeability of research micro-capsule and section salt effect, from then on aquaporin AqpZ builds the bionical diffusion barrier research of biological function prelude (ProceedingsoftheNationalAcademyofSciencesoftheUnitedStat esofAmerica as functional unit is opened, 2007,104,20719-20724).Subsequently, then Aquaporin APS of Denmark is incorporated on basilar memebrane by being first incorporated in phospholipid bilayer or in micro-capsule by functional protein, preparation is containing functional protein composite membrane (CN201180060877.4, CN201110008858.9, CN200680034784.3).Patent CN201280057206.7 is by wrapping up into phospholipid bilayer micro-capsule by functional protein, then will add in m-phenylene diamine (MPD) (MPD) solution containing the micro-capsule of aquaporin, to by and pyromellitic trimethylsilyl chloride (TMC) is monomer crosslinked is implanted to the separating effect that polyamide separating layer prepared by interfacial polymerization improves composite membrane.Functional protein embeds containing amino phospholipid bilayer by patent CN201310454532.8 and patent CN201410012030.4, and micro-capsule amino for band surface is incorporated in the substrate or surperficial electronegative substrate that dopamine modifies by covalent bond or Electrostatic Absorption, prepare functional protein composite membrane, improve the performance of diffusion barrier.
Up to the present, be all first functional protein to be incorporated in phospholipid bilayer or by the micro-capsule of phosphatide or amphiphilic copolymer self assembly based on the method preparing functional protein composite membrane in the publication of functional protein composite membrane and document, prepare composite membrane being incorporated on basalis by diverse ways.But adopt phospholipid bilayer phosphatide or by the micro-capsule of phosphatide or amphiphilic copolymer self assembly as the supporting construction of functional protein, not only its cost is high, and process is loaded down with trivial details, phospholipid bilayer phosphatide or less by embeddable functional protein content in the micro-capsule of phosphatide or amphiphilic copolymer self assembly, being incorporated into base support layer aquaporin content again can be less, therefore greatly limit the significantly raising of the bionical diffusion barrier water flux of functional protein.
Summary of the invention
For solving above-mentioned problems of the prior art, the object of the present invention is to provide a kind of composite membrane based on functional protein and preparation method thereof, utilize laminated assembling technology, directly in an assembling process functional protein is embedded in the polyelectrolyte active layer network formed by poly-zwitterion electrolyte alternating deposit, improve the embedded quantity of functional protein, and then improve the performance of functional protein composite separating film.The invention provides following technical scheme:
Based on a composite membrane for functional protein, it is characterized in that, described functional protein composite membrane is made up of the polyelectrolyte active layer and supporting layer containing functional protein;
Wherein, described polyelectrolyte active layer is obtained in support layer surface layer assembly by poly-zwitterion electrolyte, wherein functional protein dispersibles in polyanion or polycation electrolyte solution, is directly embedded in polyelectrolyte active layer in an assembling process;
Wherein, described layer assembly process is that supporting layer soaks poly-zwitterion electrolyte solution successively, washed with de-ionized water surface is used 1 ~ 3 time after each taking-up, by the electrolytical free adsorbing of poly-zwitterion or under impressed pressure or electric field action, realize its alternating deposit on supporting layer, form polyelectrolyte active layer, carry out crosslinked fixing subsequently to polyelectrolyte active layer, wherein the mol ratio of functional protein and polyelectrolyte is 0.01 ~ 100;
Wherein, functional protein is selected from but is not limited only to the one of aquaporin, ionophorous protein and carrier protein, and wherein aquaporin includes but are not limited to aquaporin 1, aquaporin 2, aquaporin 3, aquaporin 8, aquaporin-9, aquaporin z, aquaporin γ-TIP, aquaporin NIP, aquaporin PIP; Wherein ionophorous protein includes but are not limited to potassium-channel proteins, sodium-ion channel albumen, chloride channel protein; Carrier protein includes but are not limited to valinomycin;
Wherein, the polyanion electrolyte solution used in described layer assembly process includes but are not limited to polyacrylic acid (PAA), polystyrolsulfon acid (PSS), sodium alginate (SA) or polyvinylsulfonic acid (PVS) solution, the concentration of solution is 0.1g/L ~ 10g/L, the pH value of solution is greater than the isoelectric point of functional protein used, and soak time is 1min ~ 60min;
Wherein, the polycation electrolyte used in described layer assembly process includes but are not limited to polypropylene amine (PAH), diallyl dimethyl ammoniumchloride (PDADMAC), shitosan (CS) or polymine (PEI) solution, the concentration of solution is 0.1g/L ~ 10g/L, the pH value of solution is greater than the isoelectric point of functional protein used, and soak time is 1min ~ 60min;
Wherein, the number of times that described layer assembly process circulation immersion gathers zwitterion electrolyte solution is 1 ~ 100 time;
Wherein, described crosslinked fixation procedure crosslinking agent used is for containing more than one aldehyde radical, N-hydroxy-succinamide ester or epoxy radicals, and wherein crosslinking agent includes but are not limited to glutaraldehyde, paraformaldehyde, N-[α-maleimidoacetoxy] succinimide ester, two-[2-(succinimido oxygen ketonic oxygen) ethyl] sulfone, 5 (two-N-succinimido [penta ethylene glycol] esters), two succinimido glutaric acids, two succinimido suberates, γ-glycidyl ether oxygen propyl trimethoxy silicane etc.; Crosslinking time is 1min ~ 1h.
Wherein, described supporting layer be loose structure or non-apertures and surface is charged or the one of charged macromolecule or pottery or porous stainless steel mesh after surface modification;
Described functional protein composite membrane, can be used for the fields such as desalinization, sewage disposal, Dye Removal, food processing, biological medicine and disease treatment.
The present invention compared with prior art, has the following advantages and beneficial effect:
1. functional protein is embedded in the network structure that polyelectrolyte formed by the present invention in an assembling process, improves the embedded quantity of functional protein on film surface, and improves the conjugation of functional protein in active layer and stability by crosslinked;
2. the present invention adopts layer assembly method, and the procedure introducing functional protein is simple, and not by the restriction of base material, has expanded the selection of basement membrane material.
Detailed description of the invention
In case study on implementation below, the invention will be further elaborated, but the present invention is not limited thereto.
Case study on implementation 1
Polysulfones ultrafiltration basilar memebrane is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and preparation table wears the polysulphone super-filter membrane basilar memebrane of positive charge.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and PSS, the concentration of solution is 1g/L, the mol ratio of aquaporin Z and PSS is 0.01, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PEI said polycation solution 30min of 1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 15 times successively, then put into glutaraldehyde solution and be cross-linked 15min, prepare functional protein composite separating film.Adopt the water flux of dead-end filtration device test membrane under 0.1MPa pressure to be greater than 300LMH, 95% is greater than to the rejection of methylene blue dye.
Case study on implementation 2
Kynoar ultrafiltration basilar memebrane is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and the polyvinyl fluoride that preparation table wears positive charge surpasses milipore filter basilar memebrane.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and PAA, the concentration of solution is 2g/L, the mol ratio of aquaporin Z and PAA is 0.5, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PEI said polycation solution 30min of 2g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 10 times successively, then put into two succinimido suberate solution crosslinking 20min, prepare functional protein composite separating film.
Case study on implementation 3
Polycarbonate-base counterdie is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and the polyvinyl fluoride that preparation table wears positive charge surpasses milipore filter basilar memebrane.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and sodium alginate, the concentration of solution is 1g/L, the mol ratio of aquaporin Z and sodium alginate is 10, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PEI said polycation solution 30min of 1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 12 times successively, then put into paraformaldehyde solution and be cross-linked 30min, prepare functional protein composite separating film.
Case study on implementation 4
Alumina base counterdie is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and preparation table wears the alumina base counterdie of positive charge.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and PAA, the concentration of solution is 0.1g/L, the mol ratio of aquaporin Z and PAA is 50, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PEI said polycation solution 30min of 0.1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 100 times successively, then put into γ-glycidyl ether oxygen propyl trimethoxy silicane solution crosslinking 2h, prepare functional protein composite separating film.
Case study on implementation 5
Porous stainless steel nethike embrane is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and preparation table wears the alumina base counterdie of positive charge.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and PVS, the concentration of solution is 10g/L, the mol ratio of aquaporin Z and PVS is 100, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the chitosan polycation solution 30min of 10g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 8 times successively, then put into two succinimido glutaric acid solution crosslinking 10min, prepare functional protein composite separating film.
Case study on implementation 6
Polyacrylonitrile static spinning membrane is soaked after NaOH solution process the polyanion electrolyte solution containing aquaporin Z and PSS, the concentration of solution is 1g/L, the mol ratio of aquaporin Z and PSS is 0.2, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PAH said polycation solution 30min of 1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 20 times successively, then put into glutaraldehyde solution and be cross-linked 15min, prepare functional protein composite separating film.
Case study on implementation 7
Polysulfones ultrafiltration basilar memebrane is put into the dopamine Tris-HCl cushioning liquid that concentration is 2mg/mL, be placed on water bath with thermostatic control oscillator and react 6h at 30 DEG C, dopamine solution pH value is 9.0.Reaction terminates rear ethanol and deionized water rinsing film surperficial 3 times.Then by dopamine modify film put into pH value be 9.0 PEITris-HCl cushioning liquid react 6h, PEI concentration is 1g/L, and preparation table wears the polysulphone super-filter membrane basilar memebrane of positive charge.Basilar memebrane after modifying is soaked the polyanion electrolyte solution containing aquaporin Z and PSS, the concentration of solution is 1g/L, the mol ratio of aquaporin Z and PSS is 0.5, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PDADMAC said polycation solution 30min of 1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 15 times successively, then put into glutaraldehyde solution and be cross-linked 15min, prepare functional protein composite separating film.
Case study on implementation 8-10
Polyacrylonitrile static spinning membrane is soaked after NaOH solution process the polyanion electrolyte solution containing functional protein and PSS, the concentration of solution is 1g/L, the mol ratio of functional protein and PSS is 0.2, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PAH said polycation solution 30min of 1g/L again, uses washed with de-ionized water surface three times after taking out.Repeat above-mentioned immersion process 20 times successively, then put into N-[α-maleimidoacetoxy] succinimide ester or two-[2-(succinimido oxygen ketonic oxygen) ethyl] sulfone or 5 (two-N-succinimido [penta ethylene glycol] ester) solution crosslinking 15min, prepare functional protein composite separating film.
Case study on implementation 11-21
Polyacrylonitrile static spinning membrane is soaked after NaOH solution process the polyanion electrolyte solution containing aquaporin 1 or aquaporin 2 or aquaporin 3 or aquaporin 8 or aquaporin-9 or aquaporin γ-TIP or aquaporin NIP or potassium-channel proteins or sodium-ion channel albumen or chloride channel protein or valinomycin and PSS, the concentration of solution is 1g/L, the mol ratio of aquaporin 1 or aquaporin 2 or aquaporin 3 or aquaporin 8 or aquaporin-9 or aquaporin γ-TIP or aquaporin NIP or potassium-channel proteins or sodium-ion channel albumen or chloride channel protein or valinomycin and PSS is 0.2, soak time is 30min, washed with de-ionized water surface three times are used after taking out, soaking concentration is the PAH said polycation solution 30min of 1g/L again, washed with de-ionized water surface three times are used after taking out.Repeat above-mentioned immersion process 20 times successively, then put into glutaraldehyde solution and be cross-linked 15min, prepare functional protein composite separating film.
Claims (10)
1. based on a composite membrane for functional protein, it is characterized in that, described functional protein composite membrane is made up of the polyelectrolyte active layer and supporting layer containing functional protein.
2. the composite membrane based on functional protein according to claim 1, it is characterized in that, described polyelectrolyte active layer is obtained in support layer surface layer assembly by poly-zwitterion electrolyte, wherein functional protein dispersibles in polyanion or polycation electrolyte solution, is directly embedded in an assembling process in polyelectrolyte active layer.
3. the composite membrane based on functional protein according to claim 1 and 2, it is characterized in that, the layer assembly process of described polyelectrolyte active layer is that supporting layer soaks poly-zwitterion electrolyte solution successively, washed with de-ionized water surface is used 1 ~ 3 time after each taking-up, by the electrolytical free adsorbing of poly-zwitterion or under impressed pressure or electric field action, realize its alternating deposit on supporting layer, form polyelectrolyte active layer, carry out crosslinked fixing subsequently to polyelectrolyte active layer, wherein the mol ratio of functional protein and polyelectrolyte is 0.01 ~ 100.
4. the composite membrane based on functional protein according to claim 1,2 or 3, it is characterized in that, containing functional protein in polyelectrolyte active layer, functional protein is selected from but is not limited only to the one of aquaporin, ionophorous protein and carrier protein, and wherein aquaporin includes but are not limited to aquaporin 1, aquaporin 2, aquaporin 3, aquaporin 8, aquaporin-9, aquaporin z, aquaporin γ-TIP, aquaporin NIP, aquaporin PIP; Wherein ionophorous protein includes but are not limited to potassium-channel proteins, sodium-ion channel albumen, chloride channel protein; Carrier protein includes but are not limited to valinomycin.
5. the composite membrane based on functional protein according to Claims 2 or 3, it is characterized in that, the polyanion electrolyte solution used in the layer assembly process of described polyelectrolyte active layer includes but are not limited to polyacrylic acid (PAA), polystyrolsulfon acid (PSS), sodium alginate (SA) or polyvinylsulfonic acid (PVS) solution, the concentration of solution is 0.1g/L ~ 10g/L, the pH value of solution is greater than the isoelectric point of functional protein used, and soak time is 1min ~ 60min.
6. the composite membrane based on functional protein according to Claims 2 or 3, it is characterized in that, the polycation electrolyte used in the layer assembly process of described polyelectrolyte active layer includes but are not limited to polypropylene amine (PAH), diallyl dimethyl ammoniumchloride (PDADMAC), shitosan (CS) or polymine (PEI) solution, the concentration of solution is 0.1g/L ~ 10g/L, the pH value of solution is greater than the isoelectric point of functional protein used, and soak time is 1min ~ 60min.
7. the composite membrane based on functional protein according to Claims 2 or 3, is characterized in that, the number of times that the layer assembly process circulation immersion of described polyelectrolyte active layer gathers zwitterion electrolyte solution is 1 ~ 100 time.
8. the composite membrane based on functional protein according to Claims 2 or 3, it is characterized in that, the crosslinked fixation procedure crosslinking agent used of described polyelectrolyte active layer is the molecule containing being no less than Liang Ge functional group, described two and plural functional group can be same, also can be functional group not of the same race, its functional group can be but is not limited to amino, carboxyl, hydroxyl, acyl chlorides, aldehyde radical, N-hydroxy-succinamide ester, maleic anhydride, epoxy radicals, siloxanes etc., conventional crosslinking agent includes but are not limited to glutaraldehyde, paraformaldehyde, N-[α-maleimidoacetoxy] succinimide ester, two-[2-(succinimido oxygen ketonic oxygen) ethyl] sulfone, 5 (two-N-succinimido [penta ethylene glycol] esters), two succinimido glutaric acids, two succinimido suberates, γ-glycidyl ether oxygen propyl trimethoxy silicane etc., crosslinking time is 1min ~ 1h.
9. according to Claims 2 or 3 based on functional protein composite membrane, it is characterized in that, described supporting layer be loose structure or non-apertures and surface is charged or the one of charged polymeric membrane or ceramic membrane or porous stainless steel mesh after surface modification.
10. according to claim 1ly to it is characterized in that based on functional protein composite membrane, can be used for the fields such as desalinization, sewage disposal, Dye Removal, food processing, biological medicine and disease treatment.
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| CN112121644A (en) * | 2020-10-19 | 2020-12-25 | 天津工业大学 | Preparation method of oxalic acid cross-linked alginate hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
| CN112263918A (en) * | 2020-10-19 | 2021-01-26 | 天津工业大学 | Preparation method of oxalic acid crosslinked layer-by-layer self-assembled hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
| CN112263918B (en) * | 2020-10-19 | 2022-12-06 | 天津工业大学 | Preparation method of oxalic acid crosslinked layer-by-layer self-assembled hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
| CN112121644B (en) * | 2020-10-19 | 2022-12-06 | 天津工业大学 | Preparation method of oxalic acid cross-linked alginate hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
| CN115121134A (en) * | 2022-07-04 | 2022-09-30 | 重庆工商大学 | Preparation method of novel MXene-based composite membrane |
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