CN105498559B - Composite membrane based on functional protein - Google Patents

Composite membrane based on functional protein Download PDF

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CN105498559B
CN105498559B CN201511008292.4A CN201511008292A CN105498559B CN 105498559 B CN105498559 B CN 105498559B CN 201511008292 A CN201511008292 A CN 201511008292A CN 105498559 B CN105498559 B CN 105498559B
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functional protein
aquaporin
layer
composite membrane
polyelectrolyte
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CN105498559A (en
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胡云霞
刘中云
戚龙斌
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YANTAI LVSHUIFU MEMBRANE MATERIAL Ltd.
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Yantai Institute of Coastal Zone Research of CAS
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Abstract

The present invention relates to the composite membranes and preparation method thereof based on functional protein, the composite membrane is made of the polyelectrolyte active layer and supporting layer for inlaying functional protein, wherein functional protein is as functional unit, during layer assembly prepares polyelectrolyte active layer, it is directly mounted in the network structure to be formed, and its combined with firmness in active layer is improved by crosslinking curing.The preparation method operating process is simple, improves embedded quantity of the functional protein in composite membrane.The functional protein composite membrane has broad application prospects in water process and UF membrane field.

Description

Composite membrane based on functional protein
Technical field
The present invention relates to functional protein composite membrane technology fields, and in particular to a kind of to be lived by the polyelectrolyte containing functional protein Property layer composition composite membrane and preparation method, can be used for sea water desalination, sewage disposal, Dye Removal, food processing, biological medicine With the fields such as disease treatment.
Background technology
It is current restriction human civilization that there is a serious shortage in the supply for freshwater resources, energy notch is expanded rapidly and is on the rise with environmental pollution Health and the important bottleneck of sustainable development.Membrane separation technique is because of the advantages that it is efficient, energy-saving and environmental protection, in sewage disposal, seawater The fields such as desalination are by extensive use.However seperation film is deposited in preparation and application process between flux and rejection at present In " trade-off " effect, that is, the separation accuracy of film can be reduced by improving the flux of seperation film, and the rejection for improving film can drop The flux of low film.Therefore, how to break " trade-off " effect existing for traditional seperation film, while improving the flux of film and cutting Rate is stayed, preparing high-performance seperation film becomes the advanced subject in current seperation film field.
In magical nature, the cell membranes of life entity basic functional units is constituted to obtaining high osmosis and highly selective Seperation film provide valuable enlightenment.80 mid-nineties 90 of 20th century, American scientist Peter Ah Gray are found that carefully After birth aquaporin albumen, it is simply freely to expand to have verified water not being through cell membrane in a manner of high-throughput and highly selective The process of dissipating, but completed by a kind of functional protein on cell membrane.Specifically, an aquaporin AQP1 molecule is every The hydrone quantity that second can be transmitted may be up to 3,000,000,000（About 1014 cm3/s）, while can stop other nearly all Small molecule and the components such as ion（Including proton H+）.This, which is found to be, prepares high water flux seperation film and provides new approaches. 2007, aquaporin AqpZ was embedded in block by Switzerland scientist Meier W. and American scientist Kumar M. et al. for the first time Copolymer micro-capsule studies the Water permeability of micro-capsule and cuts salt effect, aquaporin AqpZ is opened as functional unit from this Build the prelude of the bionical seperation film research of biological function（Proceedings of the National Academy of Sciences of the United States of America, 2007, 104, 20719-20724）.Then, Denmark's water Functional protein by being initially introduced in phospholipid bilayer or being then introduced into substrate in micro-capsule by channel protein Co., Ltd On film, composite membrane containing functional protein is prepared（CN201180060877.4, CN201110008858.9, CN200680034784.3）.Patent CN201280057206.7 is by wrapping up functional protein into phospholipid bilayer micro-capsule, so Afterwards by containing aquaporin micro-capsule be added m-phenylene diamine (MPD) (MPD) solution in, to by with pyromellitic trimethylsilyl chloride (TMC) monomer Crosslinking is implanted to the polyamide separating layer of interfacial polymerization preparation to improve the separating effect of composite membrane.Patent Functional protein is embedded in amino-containing phospholipid bilayer by CN201310454532.8 and patent CN201410012030.4, and will Micro-capsule surface with amino is introduced into the electronegative substrate of the amine-modified substrate of DOPA or surface by covalent bond or Electrostatic Absorption On, functional protein composite membrane is prepared, the performance of seperation film is improved.
Up to the present, the side of functional protein composite membrane is prepared in the publication and document based on functional protein composite membrane Method is all functional protein to be initially introduced in phospholipid bilayer or by phosphatide or the micro-capsule of amphiphilic copolymer self assembly, It is introduced on basal layer by different methods and prepares composite membrane.However using phospholipid bilayer phosphatide or by phosphatide or parents Property copolymer self assembly support construction of the micro-capsule as functional protein, not only its is of high cost, but also process is cumbersome, double points of phosphatide Sublayer phosphatide is less by embeddable functional protein content in phosphatide or the micro-capsule of amphiphilic copolymer self assembly, is re-introduced into Base support layer aquaporin content less, therefore can greatly limit the bionical separation membrane flux of functional protein Greatly improve.
Invention content
To solve above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of based on functional protein Functional protein is directly embedded by poly- negative and positive by composite membrane and preparation method thereof in an assembling process using laminated assembling technology In the polyelectrolyte activity layer network that ionic electrolytes alternating deposit is formed, the embedded quantity of functional protein is improved, and then improve work( The performance of energy albumen composite separating film.The present invention provides the following technical solution：
A kind of composite membrane based on functional protein, which is characterized in that the functional protein composite membrane is by containing functional protein Polyelectrolyte active layer and supporting layer composition；
Wherein, the polyelectrolyte active layer is obtained in support layer surface layer assembly by poly- zwitterion electrolyte It arrives, wherein functional protein is dispersed in polyanion or polycation electrolyte solution, is directly embedded into an assembling process In polyelectrolyte active layer；
Wherein, the layer assembly process is that supporting layer impregnates poly- zwitterion electrolyte solution successively, is taken out every time Surface is cleaned with deionized water 1 ~ 3 time, make by the free adsorbing of poly- zwitterion electrolyte or in impressed pressure or electric field afterwards Under, its alternating deposit on supporting layer is realized, form polyelectrolyte active layer, then polyelectrolyte active layer is handed over Connection is fixed, and wherein the molar ratio of functional protein and polyelectrolyte is 0.01 ~ 100；
Wherein, functional protein is selected from but is not limited only to one kind of aquaporin, ionophorous protein and carrier protein, Middle aquaporin includes but are not limited to aquaporin 1, aquaporin 2, aquaporin 3, aquaporin 8, water Path protein 9, aquaporin z, aquaporin γ-TIP, aquaporin NIP, aquaporin PIP；Its intermediate ion is logical Road albumen includes but are not limited to potassium-channel proteins, sodium-ion channel albumen, chloride channel protein；Carrier protein includes But it is not limited only to valinomycin；
Wherein, the polyanion electrolyte solution used during the layer assembly includes but are not limited to polypropylene Sour (PAA), polystyrolsulfon acid (PSS), sodium alginate (SA) or polyvinylsulfonic acid (PVS) solution, solution it is dense Degree is the g/L of 0.1 g/L ~ 10, and the pH value of solution is more than the isoelectric point of functional protein used, and soaking time is the min of 1 min ~ 60；
Wherein, the polycation electrolyte used during the layer assembly includes but are not limited to polypropylene amine (PAH), diallyl dimethyl ammoniumchloride (PDADMAC), chitosan (CS) or polyethyleneimine（PEI）Solution, solution A concentration of g/L of 0.1 g/L ~ 10, the pH value of solution is more than the isoelectric point of functional protein used, and soaking time is 1min ~ 60 min；
Wherein, the number of the poly- zwitterion electrolyte solution of layer assembly process circulation immersion is 1 ~ 100 time；
Wherein, crosslinking agent used in the crosslinking fixation procedure is to contain more than one aldehyde radical, n-hydroxysuccinimide Ester or epoxy group, wherein crosslinking agent include but are not limited to glutaraldehyde, paraformaldehyde, N- [α-maleimidoacetoxy] amber Imide ester, double-[2- (succinimido oxygen carbonyl oxygen) ethyl] sulfone, 5 (double-N- succinimidos [penta ethylene glycol] Ester), two succinimido glutaric acids, two succinimido suberates, γ-glycidyl ether oxygen propyl trimethoxy silicon Alkane etc.；Crosslinking time is the h of 1 min ~ 1.
Wherein, the supporting layer be porous structure or non-apertures and band after surface is electrically charged or surface modification The macromolecule or ceramics of charge or one kind of porous stainless steel mesh；
The functional protein composite membrane can be used for sea water desalination, sewage disposal, Dye Removal, food processing, biology doctor The fields such as medicine and disease treatment.
Compared with prior art, the present invention having the following advantages and beneficial effect：
1. functional protein is embedded in the network structure of polyelectrolyte formation by the present invention in an assembling process, work(is improved Can albumen film surface embedded quantity, and by crosslinking improve conjugation and stability of the functional protein in active layer；
2. the present invention uses layer assembly method, the procedure for introducing functional protein is simple, and not by base material Limitation, has expanded the selection of basement membrane material.
Specific implementation mode
The invention will be further elaborated in following case study on implementation, however, the present invention is not limited thereto.
Case study on implementation 1
Polysulfones ultrafiltration basilar memebrane is put into the dopamine Tris-HCl buffer solutions of a concentration of 2 mg/mL, constant temperature is placed in 6 h are reacted on water bath chader at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water is used to rinse after reaction Film surface 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 h, A concentration of 1 g/L of PEI prepare the positively charged polysulfone ultrafiltration membrane basilar memebrane in surface.Basilar memebrane after modification is impregnated aqueous logical The polyanion electrolyte solution of road albumen Z and PSS, a concentration of 1 g/L of solution, the molar ratio of aquaporin Z and PSS are 0.01, soaking time is 30 min, and surface is cleaned three times with deionized water after taking-up, and the PEI that soaking concentration is 1 g/L again is poly- Cationic solution 30min cleans surface three times after taking-up with deionized water.It is repeated in above-mentioned soaking process 15 times, then puts Enter glutaraldehyde solution and be crosslinked 15 min, functional protein composite separating film is prepared.It is pressed in 0.1 MPa using dead-end filtration device The water flux of test film is more than 300 LMH under power, is more than 95% to the rejection of methylene blue dye.
Case study on implementation 2
Kynoar ultrafiltration basilar memebrane is put into the dopamine Tris-HCl buffer solutions of a concentration of 2mg/mL, is placed in 6 h are reacted in thermostatic control oscillator vibration at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water are used after reaction Rinse film surface 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 A concentration of 1 g/L of h, PEI prepares the positively charged super ultrafiltration membrane basilar memebrane of polyvinyl fluoride in surface.By the basilar memebrane leaching after modification The polyanion electrolyte solution of bubble Z containing aquaporin and PAA, a concentration of 2 g/L of solution, aquaporin Z's and PAA Molar ratio is 0.5, and soaking time is 30 min, and surface is cleaned three times with deionized water after taking-up, and soaking concentration is 2 g/L again PEI said polycation solution 30min, clean surface three times with deionized water after taking-up.It is repeated in above-mentioned soaking process 10 times, It is then placed in two succinimido suberate solution crosslinkings, 20 min, functional protein composite separating film is prepared.
Case study on implementation 3
Polycarbonate substrate film is put into the dopamine Tris-HCl buffer solutions of a concentration of 2mg/mL, thermostatted water is placed in 6 h are reacted on bath oscillator at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water flushing membrane are used after reaction Surface 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 h, PEI A concentration of 1 g/L prepares the positively charged super ultrafiltration membrane basilar memebrane of polyvinyl fluoride in surface.Basilar memebrane after modification is impregnated aqueous The polyanion electrolyte solution of channel protein Z and sodium alginate, a concentration of 1 g/L of solution, aquaporin Z and alginic acid The molar ratio of sodium is 10, and soaking time is 30 min, and surface is cleaned three times with deionized water after taking-up, and soaking concentration is 1 again The PEI said polycation solution 30min of g/L, surface is cleaned three times after taking-up with deionized water.It is repeated in above-mentioned soaking process 12 It is secondary, it is then placed in paraformaldehyde solution and is crosslinked 30 min, functional protein composite separating film is prepared.
Case study on implementation 4
Alumina base counterdie is put into the dopamine Tris-HCl buffer solutions of a concentration of 2mg/mL, water bath with thermostatic control is placed in 6 h are reacted on oscillator at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water flushing membrane table are used after reaction Face 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 h, PEI is dense Degree is 1 g/L, prepares the positively charged alumina base counterdie in surface.By after modification basilar memebrane impregnate Z containing aquaporin with The molar ratio of the polyanion electrolyte solution of PAA, a concentration of 0.1 g/L of solution, aquaporin Z and PAA is 50, is impregnated Time is 30 min, and surface is cleaned three times with deionized water after taking-up, and soaking concentration is the PEI polycations of 0.1 g/L again Solution 30min cleans surface three times after taking-up with deionized water.It is repeated in above-mentioned soaking process 100 times, is then placed in γ- 2 h of glycidyl ether oxygen propyl trimethoxy silicane solution crosslinking, is prepared functional protein composite separating film.
Case study on implementation 5
Porous stainless steel nethike embrane is put into the dopamine Tris-HCl buffer solutions of a concentration of 2mg/mL, thermostatted water is placed in 6 h are reacted on bath oscillator at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water flushing membrane are used after reaction Surface 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 h, PEI A concentration of 1 g/L prepares the positively charged alumina base counterdie in surface.Basilar memebrane after modification is impregnated into Z containing aquaporin Molar ratio with the polyanion electrolyte solution of PVS, a concentration of 10 g/L of solution, aquaporin Z and PVS is 100, leaching The bubble time is 30 min, and surface is cleaned three times with deionized water after taking-up, the poly- sun of chitosan that soaking concentration is 10 g/L again Solion 30min cleans surface three times after taking-up with deionized water.It is repeated in above-mentioned soaking process 8 times, is then placed in two 10 min of succinimido glutaric acid solution crosslinking, is prepared functional protein composite separating film.
Case study on implementation 6
Polyacrylonitrile static spinning membrane is impregnated to the polyanion of Z containing aquaporin and PSS after NaOH solution is handled The molar ratio of electrolyte solution, a concentration of 1 g/L of solution, aquaporin Z and PSS is 0.2, and soaking time is 30 min, Surface is cleaned with deionized water three times, soaking concentration is the PAH said polycation solution 30min of 1 g/L again, after taking-up after taking-up Surface is cleaned with deionized water three times.It is repeated in above-mentioned soaking process 20 times, is then placed in glutaraldehyde solution and is crosslinked 15 min, Functional protein composite separating film is prepared.
Case study on implementation 7
Polysulfones ultrafiltration basilar memebrane is put into the dopamine Tris-HCl buffer solutions of a concentration of 2 mg/mL, constant temperature is placed in 6 h are reacted on water bath chader at 30 DEG C, dopamine solution pH value is 9.0.Ethyl alcohol and deionized water is used to rinse after reaction Film surface 3 times.Then the amine-modified film of DOPA is put into the PEI Tris-HCl buffer solutions that pH value is 9.0 and reacts 6 h, A concentration of 1 g/L of PEI prepare the positively charged polysulfone ultrafiltration membrane basilar memebrane in surface.Basilar memebrane after modification is impregnated aqueous logical The polyanion electrolyte solution of road albumen Z and PSS, a concentration of 1 g/L of solution, the molar ratio of aquaporin Z and PSS are 0.5, soaking time is 30 min, and surface is cleaned three times with deionized water after taking-up, and soaking concentration is 1 g/L's again PDADMAC said polycation solution 30min, surface is cleaned three times after taking-up with deionized water.It is repeated in above-mentioned soaking process 15 It is secondary, it is then placed in glutaraldehyde solution and is crosslinked 15 min, functional protein composite separating film is prepared.
Case study on implementation 8-10
Polyacrylonitrile static spinning membrane is impregnated after NaOH solution is handled and is electrolysed containing the polyanion of functional protein and PSS The molar ratio of matter solution, a concentration of 1 g/L of solution, functional protein and PSS are 0.2, and soaking time is 30 min, is used after taking-up Deionized water cleans surface three times, and soaking concentration is the PAH said polycation solution 30min of 1 g/L again, and deionization is used after taking-up Water cleans surface three times.It is repeated in above-mentioned soaking process 20 times, is then placed in N- [α-maleimidoacetoxy] succinyl Imines ester or double-[2- (succinimido oxygen carbonyl oxygen) ethyl] sulfone or 5 (double-N- succinimidos [penta ethylene glycol] esters) 15 min of solution crosslinking, is prepared functional protein composite separating film.
Case study on implementation 11-21
Polyacrylonitrile static spinning membrane is impregnated after NaOH solution is handled containing aquaporin 1 or aquaporin 2 or Aquaporin 3 or aquaporin 8 or aquaporin-9 or aquaporin γ-TIP or aquaporin NIP or potassium from Subchannel albumen or sodium-ion channel albumen or chloride channel protein or the polyanion electrolyte of valinomycin and PSS are molten Liquid, a concentration of 1 g/L of solution, aquaporin 1 or aquaporin 2 or aquaporin 3 or aquaporin 8 or water are logical Road albumen 9 or aquaporin γ-TIP or aquaporin NIP or potassium-channel proteins or sodium-ion channel albumen or chlorine The molar ratio of ionophorous protein or valinomycin and PSS is 0.2, and soaking time is 30 min, clear with deionized water after taking-up Wash surface three times, soaking concentration is the PAH said polycation solution 30min of 1 g/L again, and surface is cleaned with deionized water after taking-up Three times.It is repeated in above-mentioned soaking process 20 times, is then placed in glutaraldehyde solution and is crosslinked 15 min, it is multiple that functional protein is prepared Close seperation film.

Claims (9)

1. a kind of composite membrane based on functional protein, which is characterized in that the functional protein composite membrane is by containing functional protein Polyelectrolyte active layer and supporting layer composition, the polyelectrolyte active layer is by poly- zwitterion electrolyte in supporting layer Surface layer assembles to obtain, and wherein functional protein is dispersed in polyanion or polycation electrolyte solution, is being assembled It is directly embedded into journey in polyelectrolyte active layer.
2. the composite membrane according to claim 1 based on functional protein, which is characterized in that the polyelectrolyte active layer Layer assembly process is that supporting layer impregnates poly- zwitterion electrolyte solution successively, and surface is cleaned with deionized water after taking out every time 1 ~ 3 time, by the free adsorbing of poly- zwitterion electrolyte or under impressed pressure or electric field action, realize it on supporting layer Alternating deposit, form polyelectrolyte active layer, crosslinking fixation then carried out to polyelectrolyte active layer, wherein functional protein with The molar ratio of polyelectrolyte is 0.01 ~ 100.
3. wanting the composite membrane based on functional protein described in 1 or 2 according to right, which is characterized in that contain in polyelectrolyte active layer Functional albumen, functional protein are selected from one kind of aquaporin, ionophorous protein and carrier protein, wherein aquaporin Including aquaporin 1, aquaporin 2, aquaporin 3, aquaporin 8, aquaporin-9, aquaporin z, Aquaporin γ-TIP, aquaporin NIP, aquaporin PIP；Wherein ionophorous protein includes potassium-channel egg In vain, sodium-ion channel albumen, chloride channel protein；Carrier protein includes valinomycin.
4. the composite membrane according to claim 1 or 2 based on functional protein, which is characterized in that the polyelectrolyte activity The polyanion electrolyte solution used during the layer assembly of layer includes polyacrylic acid (PAA), polystyrolsulfon acid (PSS), sodium alginate (SA) or polyvinylsulfonic acid (PVS) solution, a concentration of g/L of 0.1 g/L ~ 10 of solution, solution PH value be more than functional protein used isoelectric point, soaking time be the min of 1 min ~ 60.
5. the composite membrane according to claim 1 or 2 based on functional protein, which is characterized in that the polyelectrolyte is lived Property layer layer assembly during the polycation electrolyte that uses include polypropylene amine (PAH), diallyl dimethyl chlorine Change ammonium (PDADMAC), chitosan (CS) or polyethyleneimine（PEI）Solution, a concentration of g/L of 0.1 g/L ~ 10 of solution are molten The pH value of liquid is more than the isoelectric point of functional protein used, and soaking time is the min of 1min ~ 60.
6. the composite membrane according to claim 1 or 2 based on functional protein, which is characterized in that the polyelectrolyte activity The number of the poly- zwitterion electrolyte solution of layer assembly process circulation immersion of layer is 1 ~ 100 time.
7. the composite membrane according to claim 1 or 2 based on functional protein, which is characterized in that the polyelectrolyte is lived Property layer crosslinking fixation procedure used in crosslinking agent be the molecule containing no less than Liang Ge functional groups, described two and more than two Functional group can be same, or functional group not of the same race, functional group is amino, carboxyl, hydroxyl, acyl chlorides, aldehyde radical, N- hydroxyls Base succinimide ester, maleic anhydride, epoxy group, siloxanes, common crosslinking agent include glutaraldehyde, paraformaldehyde, N- [α-horse Carry out acid imide acetate] succinimide ester, double-[2- (succinimido oxygen carbonyl oxygen) ethyl] sulfone, 5 (double-N- succinyls Imido grpup [penta ethylene glycol] ester), two succinimido glutaric acids, two succinimido suberates, γ-glycidol ether Oxygen propyl trimethoxy silicane；Crosslinking time is the h of 1min ~ 1.
8. according to claim 1 or 2 be based on functional protein composite membrane, which is characterized in that the supporting layer is porous Structure or non-apertures and electrically charged after surface is electrically charged or surface modification polymeric membrane or ceramic membrane or it is porous not One kind of rust steel mesh.
9. according to claim 1 be based on functional protein composite membrane, which is characterized in that can be used for sea water desalination, at sewage Reason, Dye Removal, food processing, biological medicine and disease treatment field.
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