CN104906962B - Film for filter water - Google Patents

Film for filter water Download PDF

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Publication number
CN104906962B
CN104906962B CN201510160535.XA CN201510160535A CN104906962B CN 104906962 B CN104906962 B CN 104906962B CN 201510160535 A CN201510160535 A CN 201510160535A CN 104906962 B CN104906962 B CN 104906962B
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China
Prior art keywords
water
film
aquaporin
reverse osmosis
lipid
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CN104906962A (en
Inventor
彼得·霍姆·延森
达尼埃尔·凯勒
克劳斯·赫利克斯·尼尔森
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Aquaporin AS
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Broadcom Separation Membrane Technology (beijing) Co Ltd
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Priority claimed from CN2006800173019A external-priority patent/CN101198398B/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A kind of new moisture film is disclosed, it includes the lipid bilayer for introducing functional aquaporin.The lipid bilayer is arranged as the sandwich for including hydrophily or hydrophobic carrier material.A kind of water purifying device/system including reverse-osmosis filtering device is also disclosed, the reverse-osmosis filtering device/system includes the film with functional aquaporin.Also disclose the method for purified water and prepare the method for film.In addition, the invention provides a kind of novel perforations hydrophobic polymer perforated membrane and contain the film for introducing other transmembrane proteins rather than aquaporin.

Description

Film for filter water
The application is Chinese patent application CN201110008858.9 divisional application, and the latter is Chinese patent application CN200680017301.9 divisional application, original application correspond to international application no PCT/DK2006/000278.
Technical field
The present invention relates to a kind of new membrane, and it includes the functional aquaporin for being suitable to filtering pure water and/or glycerine (aquaporin) passage or the tetramer, filter/purification system comprising this film, and using its produce ultra-pure water and The method that excessive water is extracted from Aquo-composition.The invention further relates to novel hydrophobic polymer film.
Background technology
The various water treatment systems and method for purifying natural water source and contaminated water source have traditionally been developed, with Obtain the purified water suitable for people and/or animal edible.Moreover, semiconductor and pharmaceuticals industry have very high demand to ultra-pure water.It is super The more professional filter of the production requirement of pure water and the chemical treatment to water source.Used multiple technologies, for example, membrane filtration, from Son exchanges, submicron particle filter or nanofilter, ultraviolet light and ozone processing etc..The water of production it is very pure and containing only There are the gas such as oxygen, suspended solid and microorganism of zero to very low concentration of salt, organic principle, dissolving for example viral and thin Bacterium.But due to the factor of the continued miniaturization in such as semi-conductor industry so that the specification of ultra-pure water becomes increasingly strict.
Traditionally, water is filled by the various available water process applied designed for public and point of use (point-of-use) Put to purify or handle, such as based on following technology:Activated carbon removes organic matter;Ultraviolet disinfection;Ion exchange is except hardness (softening Water), and film desalination such as counter-infiltration (RO) or nanofiltration (NF).But in water-treatment technology field, nanofiltration is relative It is newer.NF films produce soft water by being trapped in the divalent ion of generation hardness in water.NF films allow high percent monovalence from Sub such as sodium and chlorine are by the way that while it retains the divalent ion of high percent.Because monovalent ion produces osmotic pressure, so needing In water pump is sent by RO films to high pressure.Therefore, the pressure that water is pumped across needed for film by nano-filtration membrane is much smaller, this It is because hydraulic drives power need not overcome the osmotic pressure from monovalent ion.In general, should for house and business water process Whole dissolved solids of RO films removing about 98%, and the divalent ion (hardness components of nano-filtration membrane removing about 90%:Calcium And magnesium) and about 50% monovalent ion (sodium chloride).
Two strands of current are always produced when water leaves the element using the desalter of membrane component (such as RO or NF):Desalination Product water (it has already passed through film) and effluent brine (it has passed through film surface).The abraum salt current must wash away the Yan Hekuang on film Material, to prevent it in the accumulation of film surface and fouling.It is molten if recurring the accumulation of salt and mineral in the feedwater to film The material of solution can precipitate and form solid film so that film surface scale.In addition, colloid and particulate pollutant can also adhere to film surface And cause fouling.Due to many aquatic pollutants be present, so if film irreversibly fouling or incrustation, then film can not be cleaned And it must change.This characteristic of embrane method is brought in terms of waste discharge is reduced particularly with point of use (POU) water treatment system Serious problems, point of use water treatment system is generally compact and builds as economical as possible.
Ion interchange unit is also used for softening so-called " hard water ".The problem of ion exchange water softening system, is that it passes through The hardness components (calcium and magnesium ion) of water are removed with sodium ion exchange, so as to produce so-called " soft water ".When progress ion friendship When changing the cleaning of medium, the sodium of high concentration, chlorine, the current of calcium and magnesium ion enter sewerage system, generation environment offal treatment Problem.The example of this water purification system is recorded in entitled " water purification system having plural Pairs of filters and an ozone contact chamber " United States Patent (USP) No.5, in 741,416, its disclosure A kind of water purification system, its efficient oxidation organic pollution and eliminates most of bacteriums in the current, virus and other Microorganism.It is related to dialysis membranous system selective to monovalent cation also disclosed in WO2004/099088.
Accordingly, there exist to for general family's purpose and for it is advanced research, industry and pharmacy purpose processing by or May be by the constant demand of the water purification system of the water of chemistry, biology and/or radioactive pollutant pollution.
Because water pollution or water pollution are threatened generally with the local feature of height, for example, on ship or remote mountain village or In campsite, it is therefore desirable to can readily and easily be deployed in fixation or the portable water purifying system of reality or potential pollution place System.Especially relevant is the pollutant in the water source for can effectively remove the reality such as seawater or potential pollution, suitable to produce Close the processing water that people drinks.
Because it is found that by selectively convey hydrone through biomembrane ability characterized by Spinal Cord Oedema albumen Aquaporin (aquaporin), there is certain interest in the artificial moisture film for introducing these albumen to design, referring to United States Patent (USP) Shen Please No.20040049230 " Biomimetic membranes ", its be related to description how by Spinal Cord Oedema albumen be embedded in film in reality The purifying of existing water.Described preferred form has conventional filter disc form.In order to manufacture this discharge plate, LB grooves are utilized The monolayer of thick 5nm synthesis triblock copolymer and protein is deposited on by (Langmuir-Blodgett trough) On 25mm commercialization ultrafiltration disks.Then, it is crosslinked using the ultraviolet light polymer monolayer on disk resistance to improve its Long property.The device can be tested by being installed in the room for making pressurized water source pass through film.But not on should be as The guidance of what selection synthesis triblock copolymer, also without the support data of embedded aquaporin actual functional capability.
Having itd is proposed can be by being expressed as lipid bilayer vesica by aquaporin and casting in these films more Water purification technique is innovated on the carrier of hole, referring to James R.Swartz, homepagehttp://chemenq.stanford.edu/ 01About the Department/03Faculty/Swartz/swartz.html
Present invention is primarily aimed at develop a kind of industrial water filter membrane comprising the aquaporin being introduced into film with Device, it can purify the water of highest purity, such as 100%.This can be completed currently without known technology or filter Task.
The content of the invention
On the one hand, the present invention relates to a kind of film for filter water, the film to utilize and recombinate and be converted into lipid vesicle The Spinal Cord Oedema albumen aquaporin (aquaporin) of supporting course, to form water using such as Langmuir-Blodgett methods Filter membrane.
The advantages of moisture film of the present invention, includes:Effective desalination of seawater (97-98% earth water is seawater), without Desalination chemicals and portable desalination filter is provided (one kind is similar to the dress for being capable of separation water and salt of " coffee strainer " Put), High-efficient Water purifying, durable household water/drinking water purifying and the purifying of non-electric water for semi-conductor industry, such as For third world countries.
Therefore, on the one hand, the present invention relates to a kind of moisture film, and it, which is included, has at least two perme-able support layers and separate institute State the sandwich of at least one lipid bilayer comprising functional aquaporin aquaporin of perme-able support layers.This Sample, the permeability or porous carrier will allow hydrone to reach at least one lipid pair being deposited between carrier layer through carrier Molecular layer.Then, the lipid bilayer filtered water of scattered functional aquaporin passage is included, or in aquaporin Albumen be GLpF passages in the case of also filter glycerine, make its reach offside porous carrier layer, produce the filter being made up of pure water Liquid.It is preferred that the water of this filtration is ultra-pure water (UPW), it is ion, particle, organic matter and low highly purified of colloidal content Water.The moisture film of the present invention represents the reverse osmosis membrane of new generation of most selective water carrying channel known to utilization.
Herein, " moisture film " refers to a kind of allow water by not allowing most of other materials or material to pass through simultaneously Structure.It is preferred that the moisture film of the present invention only passes through water (glycerine is passed through under certain situation) substantially, and mustn't solute and other solvents Pass through.
The second aspect of the present invention is related to a kind of moisture film, and it includes the sandwich with least two fat monolayers, When it is combined into a bilayer, the sandwich includes functional aquaporin aquaporin, and it is described at least Two fat monolayers are separated by least one perme-able support layers.In this embodiment, when carrier layer includes perforation, The perme-able support layers separate the two fat monolayers that can form lipid bilayer.
Another aspect of the present invention is related to a kind of water filtering device, and it includes the moisture film of the present invention, is optionally sealed in installation In stabilized membrane in shell, the shell has the outlet for the entrance of aqueous fluid to be purified and for purified water.
The invention further relates to a kind of method for preparing moisture film, it comprises the following steps:
A) obtain the lipid microcapsule comprising aquaporin aquaporin to steep, the aquaporin aquaporin accounts for the micro-capsule At least 0.1%mol/mol of bubble,
B) by the Vesicle fusion into planar lipid bilayer, the lipid bilayer, which is located at, has hydrophily table On the substantially planar permeable carrier in face, wherein the albumen of aquaporin covers at least 1% lipid bilayer area Domain,
C) optionally repeat step b) to obtain the bilayer of multiple fusions,
D) the second substantially planar permeable carrier with hydrophilic surface is deposited into step b) or c) middle to obtain Lipid bilayer on, to obtain sandwich, and
E) optionally the sandwich of gained is enclosed in infiltrative stabilized membrane.
The invention further relates to a kind of method for preparing moisture film, it comprises the following steps:
A) obtain the lipid microvesicle comprising aquaporin aquaporin to steep, the aquaporin aquaporin accounts for the microcapsule bubble At least 0.1%mol/mol,
B) by the Vesicle fusion into planar lipid bilayer, the lipid bilayer is assembled in hydrophobicity Around the substantially planar permeable carrier on surface, wherein the lipid bilayer of aquaporin covering at least 1% Region, and
C) optionally the sandwich of gained is enclosed in infiltrative stabilized membrane.
The invention further relates to a kind of counter-infiltration for including the moisture film (moisture film of the invention) as osmosis filtration film Water filtering device, the moisture film include functional aquaporin aquaporin.
It is used for extraction and the water filtration of recycle-water dress from such as body fluid of urine, milk and sweat the invention further relates to a kind of Put, it includes the moisture film containing functional aquaporin aquaporin.
In addition, the present invention relates to a kind of method for preparing pure water, the pure water are natural by using the water film filtering of the present invention Or contaminated water source obtains.The pure water is characterised by without the pollutant for for example dissolving material or particle.The present invention is also It is related to a kind of method for obtaining purified water, it is using the reverse osmosis membrane comprising functional aquaporin passage come filter water source.
In addition, the different aspect of the present invention is related to a kind of hydrophobic polymer film, it will be described below.
Finally, the master-plan of moisture film of the present invention is recognized as the film suitable for other purposes, wherein otherwise It is designed as the other transmembrane proteins introduced in the film of moisture film of the present invention beyond water removal channel albumen.These films are also the present invention's A part, and in addition to the selection of transmembrane protein, these films are all identical with film disclosed herein in every respect, and institute Relate to the disclosures of these films all will after necessary modification (mutatis mutatndis) be applied to containing water removal The film of other transmembrane proteins beyond channel protein.
It is selected from but is not limited to suitable for the transmembrane protein different from aquaporin of the membraned inclusions of the present invention Any transmembrane protein in transport protein taxonomy database (TCDB).TCDB can be fromhttp://www.tcdb.orgInto.
The example for the TCDB transmembrane proteins being included in the invention is:
Gas lysin passage forms toxin
Agrobacterium target host cell membrane anion channel
A- hemolysin channels form toxin
Alamethicin passage
Alginate exports PFP
Amoeba lysin
Amphiphilic peptide melittin
Amyloid b- protein peptides
Animal inward rectification K+Passage
Annexin
Apoptosis regulators
ArpQ caves albumen
AS-48
ATP gates cationic channel
Automatic transport protein
The cave albumen of hay bacillus j 29
Bacterium class III target cell stomatas
Bacterium power/permeability increasing protein
Bacteriocin AS-48 ring type polypeptides
Bacteriorhodopsin
Beticolin passages
BlyA caves albumen
Botullnus and tetanus toxin
Brucella-rhizobium PFP
The major outer membrane PFP of glycerine compound formulation
Cathilicidin
Form the Heat shock protein 70 of cationic channel
Attacin
Form the bacillus anthracis protective antigens of passage
Form the ceramide of passage
Form the colicine of passage
Form the colicine V of passage
Form the d- endotoxin insecticidal crystal albumen of passage
Form the e- endotoxins of passage
Form the leukocidin cytotoxin of passage
Chlamydia PFP
Chloride channel
The cationic channel formation of chloroplast membranes
The outer membrane solute channel of chloroplaset
Cytolysin is activated with reference to the mercaptan of cholesterol
Clostridium cytotoxin
Complement protein C9
Compound poly butyric ester-Ca2+Passage
Corynebacteria PFP
Cph1 caves albumen
C-type natruresis peptide
Cyanobacteria PFP
Cyclodextrin PFP
Cell hemolysin
Cytotoxin dextrin
Defensin
Skin bacteriostatic peptide
Diphtheria toxin
Divergicin A
Earthworm lysenin toxin
Enveloped virus E1 passages
The chloride channel of epithelium
The Na of epithelium+Passage
FadL outer membrane proteins
Fusobacterial Outer membrane protein
Form the connection albumen of gap connection
Form the innexin of gap connection
In general bacterial porins
Glucose selective OprB PFPs
The neurotransmitters receptor ion channel of glutamate gating
gp91phoxThe related cyt b of macrophage NADPH- oxidizing ferment558H+Passage
Gramicidin A passage
H+Or Na+The bacterial flagellum motor of displacement
H+Or Na+The bacterium MotAB Bacterial flagellar motors of displacement/ExbBD outer membranes transport
Breathe out bit category Outer membrane protein
HP1 caves albumen
The passage of Influenza matrix -2
Insect defensin
Intracellular chloride channel
J11 caves albumen
JAdh caves albumen
JU53 caves albumen
Laetacin X
Lacticin 481
Lactocin S
Lactococcin 972
Lactococcin A
Lactococcin G
High conductance mechanical sense answers ion channels
lholin S
The neurotransmitters receptor ion channel of part gating
LrgA caves albumen
LydA caves albumen
Magainin
Main intrinsic protein
Aptoxin bematolysis peptide
Metal-ions transportation albumen (passage)
Microcin E492
Mitochondria and plastid PFP
Mycobacteria PFP
Nisin
Non-selective cation channel -1
Non-selective cation channel -2
Form the Outer membrane protein of nucleosides specificity passage
OmpA-OmpF PFPs
OmpG PFPs
The chloride channel of organelle
The secretin of epicyte
Outer membrane auxilin
The outer membrane factor
Outer membrane pilus, which connects, draws PFP
Outer membrane protein
Outer membrane receptor
P2 caves albumen TM
P21 caves Protein S
Football rhzomorph
Phospholemman
Pilosulin
Plant defensin
The plasmodesmus of plant
Plant thionine
Lactobacillin EF
Lactobacillin JK
16kDa plastid outsourcing porin
21kDa plastid outsourcing porin
24kDa plastid outsourcing porin
Polycysteine cationic channel
Polyglutamate ion channel
Pore-forming actinocongestin
Pore-forming hemolysin E
Pore-forming RTX toxin
PRD1 caves albumen M
The fragments of peptides of prion
The cell membrane of Pseudomanas cloves HrpZ target hosts
Pseudomonad OprP PFPs
Gossypose PFP
Silk core PorCa PFPs
Blue Buddhist nun's alkali-inositol-Isosorbide-5-Nitrae, the Ca of 5- tricresyl phosphate salt acceptors2+Passage
Saponin passage
Shiga toxin B- chains
Short-chain amides and urine PFP
Small conductance mechanical sense answers ion channels
Sugared PFP
Syringomycin passage
Syringopeptin channel
T4 caves albumen
Cave albumen is immunized in T4
T7 caves albumen
The anti-peptide bacterium of horseshoe crab
Tolaasin passages
TonB-ExbB-ExbD/TolA-TolQ-TolR for outer membrane receptor (OMR)-mediation-activator
Momentary type receptor potential Ca2+Passage
Three drastic crack hemolysin BLs
Two-partner secretes PFP
Type B influenza virus NB passages
Urinate transport protein (passage)
Urine/acid amides passage
Vacuolating cytotoxin
Vibrios chitoporin/Neisseria PFPs
The ion channel Superfamily of voltage gating
The shaft-like prominent PFP of whipworm
Saccharomycete sterilization toxin K1
The cation selective Ca of yeast ext activation2+Passage
Other aspects of the present invention extract excessive water including the use of moisture film from hydrous matter or solution, such as are increased Expectation solute concentration.
Brief description of the drawings
Fig. 1 is the schematic diagram for the various parts for showing moisture film according to an embodiment of the invention, and the moisture film exists With the support lipid bilayer that aquaporin molecule is introduced in the sandwich example according to moisture film of the present invention.
Fig. 2 is the schematic diagram for the various parts for showing moisture film according to an embodiment of the invention, and the moisture film has There is the support lipid bilayer that aquaporin molecule is introduced in the sandwich example according to moisture film of the present invention, wherein wrapping The lipid bilayer of the passage containing aquaporin is located in the hole of permeability or porous carrier materials.
Fig. 3 is the schematic diagram that Biomimetic membranes of the description comprising aquaporin design.The figure show according to the present invention another The various parts of the film of embodiment, the film have the support lipid bilayer for introducing aquaporin, and the water leads to Road albumen is clipped in around voided polytetrafluoroethylene film.
Fig. 4 is the schematic diagram that Biomimetic membranes of the description comprising aquaporin design.The figure show according to the present invention another The various parts of the film of embodiment, the film have the support lipid bilayer for introducing aquaporin, and the water leads to Road albumen is clipped in around voided polytetrafluoroethylene film and is further encapsulated in sandwich.
Fig. 5 is a kind of schematic diagram for the various parts for showing moisture film, and the moisture film, which includes, introduces aquaporin Encapsulate sandwich lipid bilayer.
Fig. 6 is the schematic diagram of the encapsulating moisture film of the present invention, and now the moisture film is arranged on according to another implementation of the present invention In the filter housing with entrance and exit of scheme.
Fig. 7 is the schematic diagram for each component for showing the water purification system according to further embodiment of the present invention.The system Including following assemblies:Thick water inlet, double media filtration rooms, water softener room, wherein be optionally added bisulfites and escharotic, Reverse osmosis filter 1 and 2 (RO1, RO2), it is connected to the loop by RO1 and RO2 filters for additional purification Pump, exhaust outlet and with UV disinfection rooms storage tank.
Fig. 8 shows the aquaporin of protein and each member of water-glycerol channel protein group.
Fig. 9 is the atomic force microscopy of the film formed on mica.The film is according to the program system described in embodiment 1 It is standby.
Figure 10 shows a kind of filter of the spiral winding moisture film comprising the present invention.
Figure 11 is the cross-sectional view strength along Figure 10 line II-II interceptions.
Figure 12 is to show the schematic diagram by preparing support bilayer from air-water interface LB deposition of lipids.The left side shows Show the deposition of the first monolayer, the right shows the deposition of the second layer.
Figure 13 is the schematic diagram for showing Vesicle fusion program.Vesica is adsorbed onto on substrate and ruptured to form support bimolecular Layer.
Figure 14 is the schematic diagram for showing to prepare support lipid bilayer by spin-coating method.
Embodiment
Living cells is closed by bimolecular lamellar lipid membrane, and is separated with other cells and its extracellular matrix.Lipid bilayer The substantially impermeable water of tunic, ion and other polar molecules;However, in many cases, these entities are typically due to ring Answer extracellular or intracellular signal and need by quickly and selectively transmembrane transport.Spinal Cord Oedema task passes through aquaporin (Preston et al., 1992) is completed.Aquaporin is all most important to any type of life, and is passed through from bacterium Plant is all found into all organisms of people.Aquaporin promotes quick and high selectivity water transport, so as to allow Cell adjusts its volume and internal osmotic pressure according to the static pressure difference and/or permeable pressure head of cell membrane both sides.Water leads in human body Perhaps, the physiological significance of road albumen significantly, in kidney needs to reuptake~150- from crude urine daily in kidney 200 liters of water, i.e., the water transport that aquaporin promotes is activated when water must reclaim rapidly from body fluid.In kidney, this can Can be mainly real by two kinds of aquaporins (having 11 kinds of different aquaporins in known human body) for being referred to as AQP1 and AQP2 It is existing.In plant, aquaporin is for the water balance in the water absorption and maintenance plant of root also most important (Agre Et al., 1998, Borgnia et al., 1999).Various organisms and tissue in water transport research show, aquaporin egg There is slot in vain, it prevents any macromolecular, ion (salt) or even proton (H3O+) and hydroxide ion (OH-) flow through, simultaneously Maintain high water penetration speed;~109Molecule H2O per passage it is per second (Agre et al., 1998, Borgnia et al., 1999).Lead to until 2000 to the first high-precision 3D structure and the bacterium of related transmission glycerine that 2001 have reported AQP1 During road albumen water-glycerol channel protein GIpF (Fu et al., 2000;Murata et al., 2000;Ren et al., 2001;Sui et al., 2001), on water selective the reason for, also knows little about it.
But based on experimental configuration, it is proposed that detailed computer model, it not only explains Thief zone speed and strict Water selective, and explain aquaporin prevent proton seepage ability (de Groot and Grubm ü ller, 2001;Tajkhorshid et al., 2002, Jensen et al., 2003, Zhu et al.2003, de Groot et Al., 2003, Burykin and Warshel 2003, Ilan et al., 2004, Chakrabarti at al., 2004). Substantially, the structure of aquaporin allows hydrone and only passes through and the electrostatic adjustment control aquaporin of channel interior with single file Albumen cancels the transport (de of any salt (ion) and proton and hydroxide ion to the selectivity of any charge species Groot and Grub-m ü ller, 2001;Tajkhorshid et al., 2002, Jensen et al., 2003, Zhu et Al.2003, de Groot et al., 2003, Burykin and Warshel 2003, Ilan et al., 2004, Chakrabarti at al., 2004).In short, this means only hydrone passes through the water hole of aquaporin, others It can not all pass through.
Each shipped~10 in the passage of aquaporin9H2O molecules/second, i.e. ,~4 × 109Molecule/passage/ Second.Therefore, 1g aquaporins can transport~720 liters of water/seconds under extra-high voltage.Pass through the passage of functional aquaporin Filtering obtain water be~100% pure water, without ion, particle, organic matter and colloid, for example, by~100% H2O is formed.
The aquaporin race of memebrane protein as used herein also includes GLpF albumen, and it is also glycerine outside water removal molecule Passage.Preferable aquaporin has plant origin, such as TIP, PIP or NIP aquaporin, referring to Fig. 8.
Film of the invention disclosed below will be only by water, so as to promote purifying, desalination and the molecule of water by counter-infiltration Concentration.Known aquaporin refusal passes through all pollutants, including bacterium, virus, mineral, albumen, DNA, salt, washing Agent, the gas of dissolving and the proton even in the aqueous solution, but because its structure, aquaporin can transport water.In addition, phase Water-glycerol channel protein (GLpF) family of pass can transport glycerine.Each aquaporin includes is scheduled on film by protein anchor Interior cross-film alpha helical region and two highly conserved NPA (asparagine-Pro-Ala) rings, the ring is in protein Culminating point opposite vertexes connect, and form a kind of hourglass shape.It has been proved that the motion of water is symmetrical, and can be along any Advance in direction;The fact that it is critically important because the process not consumed energy.Due to hydraulic pressure or osmotic pressure, water is worn along specific direction Cross film.
Therefore, never drinkable water source pure water can be obtained, or if source water contains chemical substance interested, then It can optionally remove water, the expectation chemical substance of high concentration is left in input chamber.It is important that for except it is to water Other reasons outside exclusive selectivity, aquaporin are also applied for the present invention.Many member's energy of this protein families Enough bear the harsh conditions of Polluted Source Water and without loss of functionality.Aquaporin can be resisted by exposure to acid, voltage, washing Agent and thermally-induced denaturation or unfolding.Therefore, film of the invention can be used for purifying by the possible change for blocking or damaging other films The source water of Substances Pollution is learned, and it can be used in continuing the region for undergoing high temperature.
Aquaporin is also to be mutated.Because protein can be according to the gene sequence for influenceing its net shape and function Be listed in it is specific expressed in host bacteria, so technical staff can change its genetic code easily, to change the property of protein Shape.Therefore, protein can be designed as performing the expectation application different from protein Elementary Function.For example, only by general Particular amino acid residue near aquaporin center changes into cysteine, and caused aquaporin will be in binding soln Any free mercury, and terminate due to obstruction the transport of water.Therefore, these muteins used in film device can lead to Cross toxic substance concentration it is too high when simple stopping flow and detect the mercury pollution in water sample.
Finally, it is also very cheap to produce the new membrane based on protein.Comprising with the AQP1's from ox red blood cell The lipid microcapsule bubble of cell membrane fragments is cheap aquaporin source.
Alternatively, aquaporin can be from engineering Escherichia coli (E.coli) bacterial strain with the amount of milligram level Obtain.It is estimated that about 2.5mg pure protein can be obtained from producing in its every liter of culture, referring to U.S. Patent application No.20040049230。
Therefore, we be disclosed using biology assembly from the water of fouling, saliferous or other means pollution it is real The method and apparatus for now efficiently producing complete pure water.Present invention demonstrates that water transport bioprotein and external device (ED) is integrated, and refer to The production ways of water purifying device can be mass produced by going out.
The first aspect of the present invention
In the above-mentioned first aspect of the present invention, moisture film has sandwich, and the sandwich has at least two to ooze Permeability carrier layer and separate the aquaporin comprising functional aquaporin of at least two perme-able support layers at least One lipid bilayer.
Therefore, the moisture film of first aspect present invention is made up of amphipathic lipid plasma membrane, such as includes the lipid described by table 1 Film.Therefore, lipid bilayer is substantially by the amphipathic lipid selected from phosphatide, phosphoglyceride, sphingolipid and cuorin and its mixture Texture is into, such as the phosphatide such as palmityl-sn- phosphatidyl cholines (DPPC) of 1,2- bis-, or the mixture of phosphatide.
Alternatively, lipid bilayer can be made up of polymerizable lipid or containing polymerizable lipid substantially, referring to table 1.
Therefore, moisture film of the invention includes the aquaporin of the restructuring aquaporin on porous carrier.For preparing basis The useful carrier material with water-wetted surface of moisture film of the present invention is preferably selected from:Mica such as muscovite, mica tape, polysulfones, AlO2 Such as such as cellulose of the polymeric material with water-wetted surface.Carrier material is substantially plane, it means that the carrier It is preferably flat, but allow carrier that there is curvature, such as curvature required during manufacture spiral winding filter.Such case Under, carrier material is preferably flexible material, such as cellulose membrane.
The porous carrier preferably comprises the material such as mica, and it has the substantially planar structure for including water-wetted surface, And micropore or nano-pore are for example wherein formed by etching.Therefore, in the embodiment of first aspect, permeability carries Body layer include thickness be millimeter to the micron-sized substantially planar hydrophilic layer containing mica or mica tape, and be formed with The nano-pore that diameter is less than about 50 nanometers (generally in 10~40 nanometers of scope) (such as passes through etching such as track-etch technique shape Into).Mica is preferably muscovite.
The perme-able support layers can also include hydrophilic film surface, be selected from silicone film, polysulfones, AlO2Such as Cellulose etc. has the film of the polymer of water-wetted surface, is formed with diameter less than about 50 nanometers (generally at 10~40 nanometers Scope) nano-pore.
Lipid film containing aquaporin can be analogous to the bilayer of biological cell membrane natural structure, or the fat Plasma membrane can be made up of the bilayer of the lipid vesicle of multiple fused depositions.The lipid preferably has an amphiphilic, such as phosphatide (or Phosphoglyceride), sphingolipid and cuorin.When lipid layer is deposited on porous substrates, the passage of aquaporin can be with excellent Choosing deposits to hole pre-existing in carrier material nearby or in hole.
Permeability used or porous carrier are preferably according to R.M.Webber, J.L in the preferred embodiments of the invention Prepared by Anderson, M.S.John, Macromolecules 23 (1990), 1026-1034, described in it:
" film is made up of the isinglass of about 7 nanometer thickness of track-etch technique.For trace-etching-film, by using Hydrofluoric acid solution etching track as caused by the collimation fission fragment in californium 252 source forms hole.The quantity in hole is by film exposed to fission The time in source is controlled, and the radius in hole is determined by the concentration of etching period, temperature and hydrofluoric acid water-bath.The size of this some holes is equal It is even, and perpendicular to the surface of film.The uniformity in aperture is a key character of these films, because significant pore-size distribution will be by Cause the indefinite consequence of polymeric layer hydraulics thickness in the bias current by macropore.The area of section in the hole of the illuminated part of film Fraction is about 1%;Therefore, the single hole sum simulated by binomial pore-size distribution is more than 96%.Because hole is perpendicular to the table of film Face, so the length (1) in hole is equal to thickness;The thickness determines from known film size and weight.”
It is preferred that obtain final amt and the distribution in the hole roughly equal with the quantity of aquaporin in lipid layer and distribution.
The second aspect of the present invention
The aquaporin of aquaporin, the lipid bilayer assembling can also be recombinated in planar lipid bilayer Around the porous carrier film with hydrophobic surface of such as poly tetrafluoroethylene, wherein lipid monolayer is assembled in porous load The both sides of body film.In the hole of porous carrier film, lipid bilayer can recombinate the aquaporin of aquaporin by being assembled in Place.
Therefore, the second aspect of the present invention is by the moisture film structure comprising the sandwich with least two lipid monolayers Into when the lipid monolayer is assembled into a bilayer, the water that the moisture film includes functional aquaporin leads to Road, at least two lipid monolayer are separated by least one perme-able support layers.Normally, carrier layer includes and lipid Monolayer forms the hydrophobic porous material on contact surface, and wherein lipid bilayer is formed in hydrophobic porous material Hole in.
It is preferred that hydrophobic material have equivalent between deionized water drop and hydrophobic material at least 100 ° of contact angles it is hydrophobic Property, the wherein measurement of contact angle is carried out under 20 DEG C and atmospheric pressure, it is preferred that the hydrophobicity of higher degree, such as equivalent to The hydrophobic deg of at least 105 °, 110 °, 120 ° and 120 ° contact angles.Preferable hydrophobic material is parafilm or polytetrafluoroethylene (PTFE).
Hydrophobic material generally planar (but can be flexible and therefore flexible), and perforate generally in hydrophobic material It is uniformly distributed in midplane between 2 planes of material and essentially all perforation has substantially the same geometry;Close It will be provided later in the details of the perforation of hydrophobic material.
" midplane (intermediate plane) " is defined as by any surface into 2 surfaces of planar hydrophobic material The plane that the equal point of vertical range is formed.
The size of hydrophobic material middle punch should only ensure can be formed stable amphiphilic lipids bilayer in perforation, Allow them that there is nanometer, micron or millimetre-sized size.
It is maximum that hydrophobic material is preferably perforated into ratio between the perforation of material and not perforated area because this be with The lipid bilayer of aquaporin provides maximum area to realize the transport of water.The importance for the pattern being made up of perforation It is the distance between each perforation.Optimal pattern is the perforation pattern of hexagon, is had in the pattern between each perforation Minimum " wall thickness ".But, it was demonstrated that square pattern can also be enough.
Therefore, the moisture film of second aspect of the present invention is also made up of amphipathic lipid plasma membrane, such as includes the lipid described in table 1 Film.Therefore, lipid bilayer is substantially by the amphiphilic selected from phosphatide, phosphoglyceride, sphingolipid and cuorin and its mixture Lipid forms, such as the mixture of the phosphatide such as palmityl-sn- phosphatidyl cholines (DPPC) of 1,2- bis- or phosphatide.With first party The difference in face essentially consists in the film and bilayer is only formed at the region of hydrophobic carrier perforation, and to be organized as its hydrophobic for lipid End face faces aqueous environment to hydrophobic carrier and its water-wet side.
The preparation of bilayer
It must assure that the intrinsic permeability of membrane material.Material with hypotonicity will be preferred, but it must be hard simultaneously Gu and aquaporin can be introduced to form monolithic stability and fine and close 2D filter arrays.Prepared usually using various programs Support lipid bilayer.Simple technology is LB methods.Lipid soln in suitable organic solvent is spread over into Langmuir grooves In interior water parfacies and evaporation of organic solvent.Lipid film is compressed to desired table from side using a pair of moveable barrier sheets Surface pressure.Then substrate is passed perpendicularly through into film, thus the lipid layer (individual layer) of a molecule thick is transferred on substrate (see figure 12).The second monolayer can be shifted by making substrate again pass through film.It is heavy by vertical (Langmuir-Blodgett) Product method transfer total of three monolayer, still, the 4th layer of water that can utilize so-called Langmuir-Schaeffer (LS) Flat sedimentation transfer is last layer.These methods can be used together with various lipids.Primary biomembrane is typically asymmetry 's.LB and LS both provides the possibility for preparing asymmetric bilayer.This is by exchanging the lipid film in parfacies between deposition Realize.
The another way for preparing support bilayer is Vesicle fusion method (Brian and McConnell 1984).Will On the surface that the solution coating of small monolayer vesica (SUV) rives mica sheet to hydrophiling silicon chip or newly.When the sample is put When under low temperature (4 DEG C), vesica and surface merge to form continuous bilayer (Figure 13).Any theory is not limited to, it is false Determine vesica and be adsorbed onto substrate surface first, then fusion forms flat pancake shape structure, finally ruptures and deploys, on the surface Form single bilayer (Reviakine and Brisson 2000).It is also proposed that after being merged with substrate, only directly The vesicle fraction of contact substrate becomes to support bilayer (Leonenko et al.2000).By this mechanism, vesica is having The edge for having highest curvature ruptures, and the top of bilayer can subsequently migrate into the surface of substrate, the shape to increase Into support bilayer size.It has been reported that form bilayer in a few minutes in solution coating to substrate (Tokumasu et al.2003), but there may be incomplete bilayer for this short incubative time.A few hours are stayed overnight Incubation also has been reported (Reimhult et al.2003, Rinia et al.2000).
Available for prepare support bilayer the third technology be spin-coating method (Reimhult et al.2003, Simonsen and Bagatolli 2004).In spin-coating method, drop in a suitable solvent, and is placed in base by Lipid dissolution On piece, then rotary substrate, while solvent evaporates and produces lipid coatings.According to the concentration of lipid soln, spin-coating film is by one Or multiple lipid bilayers are formed.But once hydration, the multilayer are proved to be unstable, and generally there was only one Individual support bilayer retains on the surface (Figure 14).The program simple and fast, and utilize low melting point lipid (POPC) And the lipid (DPPC) with intermediate change temperature and the lipid with very high transition temperature (ceramide) are completed.Example Such as, available lipid includes phosphatide and amphiphilic lipids.
When still wanting to introducing peptide and protein in supporting bilayer, Vesicle fusion technology is applicable the most, because being carried And other programs be related to the solubilising of protein or peptide in organic solvent.Many memebrane proteins may be denatured in organic solvent, Especially if when the big functional areas that they are included are exposed in the aqueous solution of film both sides.It is therefore preferable that peptide or protein matter is inserted Enter in vesica.Before vesica is formed, peptide and protein such as aquaporin can be together with lipid in organic solvent perhaps It is molten altogether, then the vesica comprising peptide is applied on substrate.This is completed with a variety of peptides, such as WALP (Rinia et Al.2000), gramicidins (Mou et al.1996), cecropin A (van Kan et al.2003) and amyloid-beta peptide albumen (Lin et al.2001).It is preferred that otherwise by memebrane protein such as aquaporin insertion vesica.This can be utilized Reconstitution of Membrane protein enters the strategy completion of vesica, the Danielle Keller such as introduced herein paper " Supported Bilayers as models of biological membranes ", 2 months 2005, MEMPHYS-center for Biomembrane physics, Physics Department, University of Southern Denmark and Dansih Polymer Centre,The introduction of National Laboratory, Denmark chapter 4 page 41~45 In description to the cytochrome c oxidase as model protein.
The multiple-level stack of single 2D arrays is possible and may Worth Expecting.The final size of stacked array will depend on In the generally robust property and intrinsic permeability of selected membrane material/film composition.Stacking may depart from protein be slightly embedded in it is single Bilayer and be probably support bilayer at system.Then, a series of follow-up vesicas on support bilayer collapse The event of collapsing can provide multiple filtration cell arrangement, it is assumed that the prerequisite of vesica is recombinated by suitable aquaporin.By heap Folded cell arrangement introduces stabilized membrane or stabilization of polymers matrix and then sutures these individual units will be eventually through Self assembling process produces integral filter net.
The common trait of each side of the present invention
Many features are that each side of the present invention is shared:
It is according to the useful aquaporin of the moisture film of the present invention for preparing:AQP1, TIP, PIP, NIP (referring to Fig. 8) And its mixture and heterozygote.The aquaporin of plant origin is particularly desired in, because it includes such as pathogenic virus and egg The risk for the pollutant that white infection element etc. is pernicious to people is greatly reduced.In addition, the aquaporin of plant is natural plant base Because of product, and it can over-express and produce in plant.
Therefore, the aquaporin of aquaporin is preferably selected from water-glycerol channel protein (GLpF), such as GLPA passages, GLPB1 passages, GLPB2 passages, GLPB3 passages and GLPY2 passages and its mixture and heterozygote.
The moisture film of the present invention is preferably closed in stabilized permeable membrane or perforated membrane, and the film can be rigidity or flexibility , and the protection of moisture film can be served as and the prefilter of coarse particulate matter is removed from aqueous fluid to be purified.As Select or extraly, moisture film of the invention can be deposited on filter disc and form water filter.
The useful materials of stabilized membrane to being optionally used for closing moisture film of the present invention are micropore silicone film, and it has relative Less aperture simultaneously solidifies at a temperature of about room temperature or below about 50 DEG C.
Recombinated for aquaporin and the useful lipid of lipid bilayer formation is:POPC, DPPC, ceramide (referring to table 1) and its mixture.
Table 1 be for forming moisture film of the present invention used by lipid bilayer useful lipid list:
Lecithin:
1,2- dimyristoyl phosphatidyl choline (DMPC)
DPPC (DPPC)
1,2- distearyl acyl group phosphatide ester choline (DSPC)
1,2- dioleyl phosphatidyl choline (DOPC)
1,2- bis- myristoyl oleoyl (myristoleoyl) lecithin
1,2- bis- palmitoleoyl lecithin
1,2- bis- petroselinum acyl group (petroselinoyl) lecithin
1,2- bis- anti-oleoyl (elaidoyl) lecithin
1,2- bis- sub-oleoyl lecithin
1,2- bis- linolenyl (linolenoyl) lecithin
1,2- bis- eicosylene acyl group (eicosenoyl) lecithin
1,2- bis- arachidonic acid acyl group lecithin
1,2- bis- mustard acyl group (erucoyl) lecithin
1,2- bis- tetracosa carbon enoyl- (nervonoyl) lecithin
1- palmityl -2- oleoyls lecithin (POPC)
1- palmityl -2- sub-oleoyl lecithin
1- palmityl -2- arachidonic acid acyl group lecithin
The dodecahexaene acyl group lecithin of 1- palmityls -2- two
1- stearyl -2- oleoyls lecithin (SOPC)
1- stearyl -2- sub-oleoyl lecithin
1- stearyl -2- arachidonic acid acyl group lecithin
The dodecahexaene acyl group lecithin of 1- stearyls -2- two
1- oleoyl -2- palmityl lecithin
1- oleoyl -2- stearyl lecithin
1,2- bis- two dodecahexaene acyl group lecithin
Phosphatidyl-ethanolamine:
1,2-dimristoyl phosphatidylethanolamine l (DMPE)
1,2- DPPE (DPPE)
1,2- DSPE (DSPE)
1,2- DOPE (DOPE)
1- palmityl -2- oleolyl phosphatidyls monoethanolamines (POPE)
1 palmityl -2- sub-oleoyl phosphatidyl-ethanolamines
1- palmityl -2- arachidonic acid acylphosphatidyl ethanolamines
The dodecahexaene acylphosphatidyl ethanolamines of 1- palmityls -2- two
1- stearyl -2- oleolyl phosphatidyls monoethanolamines (SOPE)
1- stearyl -2- sub-oleoyl phosphatidyl-ethanolamines
1- stearyl -2- arachidonic acid acylphosphatidyl ethanolamines
The dodecahexaene acylphosphatidyl ethanolamines of 1- stearyls -2- two
1,2- bis- anti-oleolyl phosphatidyl monoethanolamine
1,2- bis- sub-oleoyl phosphatidyl-ethanolamine
1,2- bis- linolenyl phosphatidyl-ethanolamine
1,2- bis- arachidonic acid acylphosphatidyl ethanolamine
1,2- bis- two dodecahexaene acylphosphatidyl ethanolamine
1,2- bis- palmitoleoyl phosphatidyl-ethanolamine
Phosphatidyl glycerol:
1,2- DMPG (DMPG)
1,2- DPPG (DPPG)
1,2- DSPG (DSPG)
1,2- DOPG (DOPG)
1- palmityl -2- oleolyl phosphatidyls glycerine (POPG)
1- palmityl -2- sub-oleoyl phosphatidyl glycerols
1- palmityl -2- arachidonic acid acyl phospholipids acyl glycerine
The dodecahexaene acyl phospholipids acyl glycerine of 1- palmityls -2- two
1- stearyl -2- oleolyl phosphatidyls glycerine (SOPG)
1- stearyl -2- sub-oleoyl phosphatidyl glycerols
1- stearyl -2- arachidonic acid acyl phospholipids acyl glycerine
The dodecahexaene acyl phospholipids acyl glycerine of 1- stearyls -2- two
Phosphatidylserine:
1- palmityl -2- oleolyl phosphatidyl Serines (POPS)
1- palmityl -2- sub-oleoyl phosphatidylserines
1- palmityl -2- arachidonic acid acyl phospholipids acyl serines
The dodecahexaene acyl phospholipids acyl serines of 1- palmityls -2- two
1- stearyl -2- oleolyl phosphatidyl Serines (SOPS)
1- stearyl -2- sub-oleoyl phosphatidylserines
1- stearyl -2- arachidonic acid acyl phospholipids acyl serines
The dodecahexaene acyl phospholipids acyl serines of 1- stearyls -2- two
1,2- bis- myristoyl phosphatidylserine (DMPS)
1,2- DPPS (DPPS)
1,2- DSPS (DSPS)
1,2- dioleoyl phosphatidylserine (DOPS)
1,2- bis- two dodecahexaene acyl phospholipids acyl serine
1,2- bis- mustard acyl phospholipids acyl serine
Special lipid:
Cuorin
Bipolarity lipid
Natural lipid extract:
Egg yolk lecithin
OX-heart lecithin
Brain lecithin
Beef liver lecithin
Soybean lecithin
Escherichia coli (E.Coli) phosphatidyl-ethanolamine
OX-heart phosphatidyl-ethanolamine
Brain phospholipid acyl monoethanolamine
Beef liver phosphatidyl-ethanolamine
The phosphatidyl-ethanolamine of egg
Beef liver phosphatidylinositol
Soybean phospholipid phosphatidyl inositol
Brain phospholipid acyl serine
Soy phosphatidylserine
Polymerizable lipid:
1,2- bis- -10,12-tricosadiynoyl-sn- glycero -3- phosphocholines (DTPC)
1,2- bis- -10,12-tricosadiynoyl-sn- glycero -3- phosphoethanolamines (DTPE)
1- palmityls -2,10,12-tricosadiynoyl-sn- glycero -3- phosphoethanolamines (PTPE)
(DC8,9PC [1,2- double (10,12-tricosadiynoyl)-sn- glycero -3- phosphocholines]
Two PhyPC [1,2- bis- phytane acyl group (phytanoyl)-sn- glycero -3- phosphocholines]
Water treatment system and water filtering device
In one embodiment, the present invention has the form of conventional filter disc, because it is easy to detection functionality.In order to make This discharge plate is made, the immobilized artificial membrane bilayer of the protein comprising functional aquaporin is deposited into 25mm commercializations by LB grooves In ultrafiltration panel surface.In a preferred embodiment of the invention, moisture film spiral winding optionally together with conventional film forms spiral and twined Around RO modules, referring to Figure 10 and 11.
Filter disc is arranged in the confined chamber with entrance and exit, such as the filter disc at the water source with pump is connected to through pipe Room, the pump make the source water of pressurization be flowed out through film and from outlet.When only pure water passes through the opposite side of film, and pollute solute When keeping high concentration in originating room, then it is assumed that the device possesses function.Contaminated solution must be pressurizeed, to overcome stream of pure water Enter the natural tendency in the compartment of the room with more dissolved particles, so as to overcome the osmotic pressure of water, be about for drinking water 10psi.The purpose of moisture film of the present invention is counter-infiltration and pure water is separated with pollution solute.This trend or osmotic pressure of system can Represented with pound per square inch (psi).For example, the osmotic pressure of seawater is 360~400psi.
There is several methods that available for the pressure for allowing the device to bear these types.A kind of method is to add the nothing of high concentration The poison and solute that easily removes is into new Water Room, with the normal osmosis of the promotion cross-film when the pressurization due to room also counter-infiltration occurs Pressure.Moreover, pressure needed for counter-infiltration can also pass through the cascade in the sealed connection room of the pollutant continuously reduced comprising concentration It is middle to be reduced using multilayer aquaporin film.Synthesis pressure in each pair room needed for purified water is stagnation pressure necessary to counter-infiltration A part for power.Therefore, each film is only subjected to small pressure, so as to be remained intact with larger chance.Therefore, if each pair Concentration difference between room only has 10%, rather than 100%, then in each junction, purifying source water only needs 10% above-mentioned height Pressure.Pure water is by the continuous production in the final stage room of pressure and flow constant.
Aquaporin reverse osmosis membrane can only purifying contains the water of several different type pollutants in one step.Tradition High purity systems need that several parts of water softener, carbon filter, ion-exchanger, UV or chemical disinfection can be included, and The dual channel reverse percolating filter being used in combination is set, then could produce purified water.This complex appts can not be such as aquaporin Protein film equally removes the gas of dissolving or the material less than 150 dalton.In addition, all these parts need to safeguard.UV lamp Bubble needs to change and energy.Ion-exchanger needs chemical regeneration when saturated.Softening agent needs salt.Carbon and reverse osmosis cartridge are being tied It must be changed when dirty.Finally, single step device will require the space far below typical purification system and weight, and this advantage can Realized by the portable unit of the moisture film comprising aquaporin of the present invention.
Aquaporin film is also than conventional system faster.Conventional high speed reverse osmosis units are per minute can to produce about 28.4 Rise the clean water of (7.5 gallons).Current research shows that hydrone is satisfied with the rate motion of 54 μm of ol/ seconds through aquaporin Lipid film (the 0.0177mm of sum2).(Pohl, P., Saparov, S.M., Borgnia, M.J., and Agre, P., (2001), Proceedings of the National Academy of Sciences 98, p.9624-9629).Therefore, surface area is 1.0m2The theoretical aquaporin reverse osmosis membrane pure water per minute that can filter up to 3295 liters.This speed is normal 116 times of purification devices.
Another aspect of the invention is related to a kind of water treatment system, and it is therefrom removing chemistry, radioactivity, biology And/or particulate pollutant, the system includes the monoblock type shell that entrance is arranged to connect external water source, wherein outside the monoblock type One or more water filter units for including moisture film of the present invention are disposed with shell, the moisture film is arranged comes from external water for handling The water in source is to produce ultrapure current, and wherein the monoblock type shell includes being used for the outlet for therefrom discharging the ultra-pure water.This The example of kind processing system is reverse-osmosis filtering device.
But moisture film of the invention can also be replaced with other films comprising functional aquaporin, such as US That is instructed in 2004/049230 includes the film of aquaporin.Definite property regardless of the film comprising aquaporin, phase Believe that this water treatment system described herein and filter for installation are creative with the ability of its own.
Therefore, present invention additionally comprises for the reverse osmosis water filter from saline source production desalted water, the desalted water Available for agricultural irrigation and/or drinking water, wherein at least one final reverse osmosis filter membrane has been replaced with comprising feature water The moisture film of channel protein aquaporin, film of the invention.Similarly, present invention additionally comprises produce the anti-of ultra-pure water from thick water source Osmosis water filtering device, the ultra-pure water can be used for semi-conductor industry and/or pharmaceuticals industry, wherein at least one final reverse osmosis Filter membrane has replaced with this moisture film of the moisture film comprising functional aquaporin aquaporin.The invention further relates to one kind to be used for From for municipal water industry, chemical industry, drinking water indus, food industry, electronics industry, oil and gas industry, rendering industry, paper The reverse osmosis water filter of thick water source production pure water used in slurry and paper industry, metal industry, mining industry and power industry, its In at least one final reverse osmosis filter membrane replaced with this moisture film for including functional aquaporin aquaporin.Generally, Osmotic pressure is applied to the downstream of the moisture film to drive water to flow.The osmotic pressure is more than water to be purified usually from osmotic pressure The concentrated solution in source.
It is used for extraction and the water filtration of recycle-water dress from body fluid such as urine, milk and sweat the invention further relates to a kind of Put, it includes the moisture film of the aquaporin containing functional aquaporin, moisture film of the invention.
Water purification system/filter of the present invention may also include the particle filtering module of moisture film device upstream, and it is used for Pre-process current and therefrom remove at least part particulate pollutant.
The function of this particle filtering module is to mitigate the burden of downstream water filtering device so that needed for current fully flow Pressure it is relatively low, so as to optimize the energy consumption of whole system and improve its operational efficiency.
Particle filtering module preferably includes one or more selected from (a) hollow fiber membrane separator and (b) ultra-filtering element Filter element.Multiple hollow fiber membrane separators and ultra-filtering element can use over-over mode to use, so that this particle filtering mould The particle removal ability of block maximizes.
Filter element preferably includes slipstream well known in the art or cross-flow filtration device, to prevent the stifled of filtering surface Plug.
In order to which the vulnerability of this particle filtering module to be reduced to the failure of single filter, and it is single in order to reduce System down time during filter cleaning and maintenance, this particle filtering module preferably include the filtering of multiple parallel arrangements Element, wherein each element provides independent filtration path for current.
This particle filtering module is preferably used in preliminary filter upstream, such as it there can be about 10 μm to about 20 μm Porosity, to filter out the bulky grain in current (such as solid particle, spore and bacterium), and extend downstream particulate filter module The life-span of filter device therefor in block.
This pollutant removal unit can include nanofiltration (NF) module or anti-for being used for removing the ion in current Permeate (RO) module.RO modules conventionally used for this purpose and are proved to effective.In addition, compared with RO modules, nanometer mistake Filter needs relatively low pressure and less energy and water consumption.
The water treatment system of the present invention can also include handled water and flow into hydraulic pressure storage groove therein, to maintain in system Uniform pressure simultaneously provides substantially invariable water supply for the water consumption factory in downstream.
The water treatment system of the present invention can also include water quality monitoring module, and its continuous monitoring one or more indicates to wait to locate The variable for managing effluent quality (such as includes but is not limited to:Cl concn, pH value, electrical conductivity, total organic carbon, dissolved oxygen, biochemical oxygen demand Amount, turbidity and radioactivity), these variables are compared with the baseline value that the advance observation by these variables determines, identified And the notable deviation of these baseline values, and produce the output signal for indicating the deviation.Automated sensor can be used for accurate measurement These variables, and sampler can be used for the discrete water sample of conventional Christmas, and this allows sample and time when there is deviation Framework apart.Then various analysis programs can be implemented to the sample, to identify the pollutant for causing this deviation in water.The water Matter monitoring modular can also be run to be switched on or switched off water treatment system as needed, and/or warning authorities water quality do not meet it is pre- Fixed drinking water quality standard.
The water treatment system of the present invention can be fixed or portable.It is preferably built and arranged for vehicle transport And deployment, so that it can be used for distally supplying water.
The system of the present invention can configure various assemblies by the way of parallel and/or series redundancy, can to improve system By property and the performance of whole system., it will also be appreciated that system described herein and embodiment can use functional redundancy with reality The complete removal of existing water pollutant.
System/water filtering device can be used for purified water, and as described above, the present invention is also related to really prepares purified water Method, wherein methods described include the systems/devices for passing water through the present invention.The water being achieved in that will for example be substantially free of from Son, particle, organic matter and colloid, because these parts have been trapped in device.
The hydrophobic membrane of the present invention
As described in the above disclosure of second aspect of the present invention, i.e., moisture film can be in the centre that lipid monolayer surrounds Hydrophobic material is included in supporting layer, the material of hydrophobic form membrane can be prepared, the hydrophobic membrane, which includes, has uniform shape and chi Very little equally distributed perforation.Believe that this hydrophobic membrane itself is creative.
Therefore, the invention further relates to the hydrophobic polymer film comprising multiple perforation, wherein the perforation is evenly distributed on film In, and essentially all perforation has substantially the same geometry in the midplane between 2 planes of hydrophobic material. When these perforation are respectively provided with large enough to allow vapor by but small enough to when preventing the aperture area that aqueous water passes through, Such as 100nm2~1mm2Area when, the film will produce with for exampleThe equivalent effect of material, i.e., the film can With ventilative but waterproof.Believe the film of the present invention better than such asMaterial because perforation size and geometric form Shape is by good control.
Term " hydrophobic membrane " herein refers to substantially planar hydrophobic material.The film is typically flexible so that plane Material can obtain the form (if i.e., material is wrapped around the shaft) of curved surface, so that the hydrophobic membrane is suitable as clothing and other soft A part for fabric in property structure.
The perforation generally has greatest cross-section length of the nanometer to millimeter scope, such as micrometer range, and the film leads to Often with there is thickness of the millimeter to micron.
Generally, the geometry of perforation is selected from circular and ellipse.When introducing perforation in film using laser equipment, two Kind of shape is all readily available-for example, circular hole can utilize static laser beam to obtain, and film is relative to laser beam during exposure Motion (by moving film or laser beam) oval or even bar-shaped hole will be provided.In preferred embodiments, perforate It is respectively provided with essentially identical size.Membrane material is generally selected from the above-mentioned hydrophobic material related to the disclosure of second aspect of the present invention Material.
When with reference to particular of the present invention to describe the present invention, it is to be understood that many changes, modification and embodiment party Case is possible, therefore all these changes, modification and embodiment will be understood as within the spirit and scope of the present invention. All references file is fully incorporated herein by quoting.
By disclosure below and appended claims, other side of the invention, feature and embodiment will more fill That divides is obvious.
Embodiment 1
AQP-1 (proteoliposome) restructuring in DPPC lipid vesicles
The moisture film according to the present invention is prepared using following procedure
1. the preparation (SUV) of small monolayer vesica
A. by dry DPPC lipid suspensions in milli-Q water to obtain 1.3~1.5mM concentration.
B., suspension is incubated to hydration in 1 hour at 55 DEG C and obtains polymolecular layer vesica (MLV)
C. by the way that through two 100 nanometers of polycarbonate filter 12 times prepared by MLV Solution extrusions into SUV
D. SUV solution is preserved at 55 DEG C.
2.BioBeadsTMThe preparation of (polystyrene bead)
A. milli-Q water washings about 4g BioBeads are usedTM5 times
B. by scrubbed BioBeadsTMThe sonication 1 hour under water suction
3. restructuring
A. the SUV solution of proper volume is moved into eppendorf pipes with pipette
B. 50 μ l 20% Triton X-100 are added
C. 10 μ l AQP-1 (concentration 0.5mg/ml) of denatured form in phosphate buffer are added thereto, the AQP-1 The method described according to Zeidel et al. (1992) purifies
D. milli-Q water is added to the μ l of final volume 200
E. Incubation solution, and shaking 15 minutes at room temperature
F. BioBeads scrubbed about 75mg is added in solution, then incubates and shake 30~45 minutes
G. the solution is moved into clean Eppendorf pipes with pipette
H. repeat step f~g 3 times (totally four times of BioBeads)
I. the lipid protein liquid solution is standby
Fig. 9 shows AFM (AFM) photo of DPPC films on muscovite, and shows the AQP- recombinated in DPPC films 1, it shows the support bilayer for having completed recombination and gained vesica.Such as measure obtained by image, the small ring in image Shape structural area is about 36nm2.This meets very much with the protein surface area in lipid bilayer.(come from an average 6 various sizes of images of three different zones), the surface of protein covering 48%, and the surface of lipid covering 52%.It is false It is 0.5nm to determine lipid area2, then the lipid-protein ratio (LPR) calculated is 77.Support bilayer is 50 by LPR Proteoliposome Vesicle fusion is made.
Embodiment 2
Lipid bilayer and possible other multiple bilayers are formed on porous muscovite, is illustrated with obtaining Fig. 1 such as Moisture film shown in property.
1. by white clouds master slice (about 1cm2) rived with band
2. immediately by 25 μ l proteoliposomes solution coatings in embodiment 1 to mica surface after riving.
3. sample is incubated 10 minutes to form the bilayer of fusion for (21 DEG C) at room temperature.
4. after incubating, with milli-Q water washings sample 7 times, to remove excessive uncombined vesica.
5. finally newly rive second muscovite is deposited on formed lipid bilayer.
Embodiment 3
AQP-1 restructuring in E.Coli lipid-soluble extract vesicas
E.coli wholes lipid-soluble extract in chloroform derives from Avanti Polar Lipids (Alabaster, AL). Solvent (chloroform, ethanol, methanol, decane) is all purchased from Sigma-Aldrich (St.Louis, MO).SM-2BioBeads is purchased from BioRad Laboratories (Hercules, CA).Water in all preparations is ultrapure milli-Q water (18.2M Ω cm-1)。 By ox red blood cell purify aquaporin -1 as unfolded protein suspension by University ofAarhus' Dr.Jan Enghild are obtained.
Evaporate chloroform from lipid soln, and dry lipid is hydrated 30 minutes at 55 DEG C with 100mM KCl.Stir molten Liquid, and by making solution in Lipex extruders (Northern Lipids, Vancouver, CD) through two 100nm's Polycarbonate filter forms small monolayer vesica (SUV) 12 times.By adding Triton X-100 (Sigma) to 1.25% (wt/vol) final solubility and then to add AQP-1 to lipid-protein ratio (LPR) be made recombinate mix at 1000: 1 Thing.Proteoliposome is formed by removing detergent.This can be realized by being adsorbed onto on hydrophobic BioBeads (SM-2).Fat Proteosome can on the day of preparation or latter day use.Between experiment, solution preserves at 4 DEG C.
Embodiment 4
The formation of plane bi-layer membrane and voltage clamp experiment:AQP-1 is introduced into lipid bilayer without increasing ion Conductivity
Voltage clamp is by the potential V controls (or " clamping down on ") of bilayer (or cell membrane) in desired level.It is used herein Method measurement cross over two aqueous solution between spacer at formed bilayer potential.The silver electrode for scribbling AgCl is put In one chamber, the voltage and voltage to be maintained (referred to as dominating voltage) and are electrically compared.Then clamp down on circuit pass through it is another Electrode returns to electric current in another room.Even if facing infiltrative change, the feedback circuit also will across bilayer potential dimension Hold in desired level.Most of all, the device allows measurement simultaneously that across bilayer potential is maintained at into given voltage institute The electric current I needed.Therefore, how voltage clamp technology instruction membrane potential influences transmembrane ion electric current.The influence is with current-voltage (I/ V) relation represents.
Plane bilayer by E.coli (Avanti Polar Lipids, Alabaster, AL) n-decane solution (2.5%wt/vol) passes through the hole (diameter 1.3mm) in Teflon spacers to be formed, and the spacer prepares experimental day Two kinds of non-cushioned 0.1M KCl aqueous solution isolation.By using scribbling AgCl silver wire as electrode at 22 DEG C AxoPatch200 amplifiers (Axon Instruments, Sunnyvale, CA) complete bilayer I/V experiments.Establish I/V associations View, and utilize the softwares of Clampex 9.2 (Axon Instruments, Sunnyvale, CA) record data.The data utilize eight Pole Bessel filter (Bessel filter) (Frequency Devices, Haverhill, MA) is 500Hz's (- 3dB) LPF under angular frequency, and carry out 16 AD conversion (DigiDatal332A, Axon Instruments, Sunnvale, CA it is stored in after) in PC (Dell Computer, Austin, Texas) and is used to analyze.Analyze data, and pass through ClampFit 9.2 (Axon Instruments, Sunnyvale, CA) and OriginPro 7.5 (OriginLab, Northhampton, MA) Display.
With stereoscope (Zeiss) the monitoring bilayer equipped with cold light source (IntraLux 5000, Volpi, CH) Formed.After in hole of the lipidosis in spacer, the newton diffraction color of lipid polymolecular layer fades away, and at 10 minutes Transparent " black " lipid film surrounded by thicker lipid/decane annulus is formed afterwards.This desalination also be reflected in zero potential IRMS Under across in the temporary transient change of the root mean square of bilayer electric current.Initial IRMS is about 1.6pA, then rises to about 6pA steady-state value, This instruction forms stable bilayer.A diameter of about 1200 μm of the bilayer.After bilayer is formed, stepping is utilized Agreement obtains across bilayer electric current, and wherein potential steps to+90mV with 10mV increment from -100mV.Each step continues 1000ms, it is 1000ms between step.
After the vesica containing AQP-1 is added into bimolecular layer forming liquid (2: 1vol/vol), AQP-1 is introduced into plane In bilayer, similar result is obtained.
AQP-1 introduces lipid bilayer and does not change gas current, but compared with the control, that it changes include AQP- The time constant of 1 bilayer.For first approximation, latter observation may be interpreted as annulus and effective dielectric of bilayer is normal Several changes.This is possible, because compared with hydrocarbon materials, the relatively low dielectric constant of AQP-1 protein materials will cause double Relatively low time constant in both molecular layer and annulus.
Embodiment 5
Osmotic gradient is tested:The AQP-1 being introduced into lipid bilayer produces osmotic gradient, causes hypotonic side not stir layer Interior ion concentration increase
After the lipid bilayer containing AQP-1 is formed, K in layer is not nearby stirred by measuring film+Ion concentration Change observes the cross-film water flux of osmotic pressure driving.
According to Zeuthen technology, two-tube K is manufactured using 1.2mm OD capillary glass tubies (Corning120F)+Electrode.
PC is connected to by using 12 BioLogic 1401+AD/DA interfaces (Biologic, Claix, France) The DUO773 amplifiers (WPI) of (Dell Computer, Austin, TX) are recorded from two-tube electrode voltage.
By two-tube electrode be placed in containing useful 20mM tri- [methylol]-aminomethane hydrochloride (TRIS) (T3253, Sigma, St Louis, MO) buffering pH 7.2 100mM KCl rear (suitable) room in recorded.Electrode holder is installed, makes electrode phase Stretched into for aqueous solution surface angle at 45 ° in suitable room, and utilization hydraulic pressure narishige (David Knopf Instruments, Model 1207B) manipulate, minimum step is 0.25 μm.The formation of bilayer and the coarse positioning of electrode utilize 5.3 section descriptions Stereoscope monitors, and the start recording after lipidosis 10~20 minutes.The overall accuracy of bilayer electrode distance It is adjusted to about ± 7 μm, and absolute distance is adjusted by being in close contact the significantly change of electrode potential after bilayer.Across double The osmotic gradient of molecular layer by the pH 7.2 that is buffered containing useful 20mM TRIS containing 4M ureas (452042V, BDH, Poole, UK KCl solution induction in (anti-) side produces before).
It was observed that in the case where across bilayer osmotic gradient be present, the lipid bilayer for introducing AQP-1 induces water Flowing.
With body K+Concentration is compared, and when osmotic gradient be present, the AQP-1 being introduced into lipid bilayer makes K+Ion is dense Degree is in hypotonic side away from adding about 8% in the μ m of bilayer 20.
Film can bear 4M osmotic gradient.
Embodiment 6
Include the UPW systems of the film according to the present invention
The water purification system of the displays of Figure 10 and 11 according to an embodiment of the invention.Figure 10 is that the perspective section of element is shown It is intended to, and Figure 11 is the cross-sectional view strength along Figure 10 line II-II incisions.
The element has the hollow tube 1 for being arranged in element center, and its surface is formed with several through hole 1a.Reverse osmosis membrane 2nd, penetrating fluid channel membrane 3 and the mode described below of feed channel film 4 are wound around the outer surface of hollow tube 1.
Each reverse osmosis membrane 2 is overall to have bag-shaped shape, and penetrating fluid channel membrane 3 is disposed therein.Bag-shaped reverse osmosis Permeable membrane 2 is connected to the outer surface of hollow tube 1, while its 2a that is open is enclosed in the through hole 1a formed in hollow tube 1 so that counter-infiltration The inside of film 2 and penetrating fluid channel membrane 3 connect with through hole 1a.
Each feed channel film 4 is arranged between coupled reverse osmosis membrane 2, and is configured to allow liquid to pass through Framing component 5 therein is connected to the both ends of film and channel components, is derived from helical structure.
Said elements are arranged in pressure vessel, and suitable for supplying feeding liquid from its one end (upstream side) under a predetermined 6。
When feeding liquid 6 flows along feed channel component 4, it is separated into by the reverse osmosis separation of reverse osmosis membrane 2 Penetrating fluid and solute.Through reverse osmosis membrane 2 and the penetrating fluid with low solute concentration flows into through hole 1a and collects in hollow tube 1 In.Then penetrating fluid 6a is taken out from the downstream of element.
The feeding liquid for being not passed through reverse osmosis membrane 2 continues to flow to downstream along feed channel component 4.During flow, Feeding liquid, which absorbs, to be separated from feeding liquid and stays in the solute on film surface, so as to become the concentrate 6b with high solute concentration.
There is a key issue in operating element, i.e. element function is reduced due to concentration polarization.
Concentration polarization is that the impurity that is included in a kind of scale forming matter such as feeding liquid and enriching pollutants lead to feeding liquid The surface for the reverse osmosis membrane 2 that road component 4 contacts and make it that the concentration of solute and scale forming matter showing higher than film surface in feeding liquid As.As a result, osmotic pressure raises.
When there is concentration polarization, the amount of penetrating fluid is reduced, and the contamination precipitation such as gel and incrustation scale is on film surface. Therefore, reverse osmosis membrane can not develop its capacity, and the performance of element then reduces.
The generation of concentration polarization can be suppressed by the turbulent flow of feeding liquid on the surface of the film.For example, by using thickness Less feed channel component 4 to increase the linear velocity of the enterprising feed liquid in film surface is easier that turbulent flow occurs so that concentration polarization Layer can be with thinning.
But because feed channel component 4 has less thickness so that limited by feed channel component 4 logical Road is easily blocked by such as impurity of the scale forming matter in feeding liquid and Institute of Micro-biology.As a result, element function reduction and feeding liquid In the pressure loss increase.In order to keep the quality and quantity of penetrating fluid, the operating pressure of feeding liquid needs to improve, it is therefore necessary to provides The high-pressure pump and high-voltage tube of operation power are needed, it causes the increase of liquid production cost.
At least one reverse osmosis membrane is to include aquaporin and/or water-glycerol channel protein passage according to the present invention Moisture film.
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The original claims that herein below corresponds in original application:
1. a kind of moisture film, it includes the sandwich with least two perme-able support layers, at least two infiltration Property carrier layer is separated by least one lipid bilayer comprising functional aquaporin aquaporin.
2. according to the moisture film of item 1, the lipid bilayer is substantially by selected from phosphatide, phosphoglyceride, sphingolipid and heart phosphorus The amphiphilic lipids of fat and its mixture are formed.
3. according to the moisture film of item 2, wherein the amphiphilic lipids are DPPC or other phosphatide or its mixture.
4. according to the moisture film of item 1, wherein the lipid bilayer is made up of polymerizable lipid substantially.
5. according to the moisture film of any one of foregoing item, wherein the perme-able support layers are included containing mica or mica tape Substantially planar and thickness be millimeter to micron-sized hydrophilic layer, and be formed with diameter less than about 50nm nano-pore.
6. according to the moisture film of item 5, wherein the nano-pore is formed by track-etch technique.
7. according to the moisture film of item 5 or 6, wherein the mica is muscovite.
8. according to the moisture film of any one of foregoing item, wherein the perme-able support layers include hydrophilic film surface, such as Selected from silicone film, polysulfones, AlO2With the film of such as cellulose of the polymer with water-wetted surface, it is formed with diameter and is less than About 50nm nano-pore.
9. according to the moisture film of any one of item 5~8, wherein a diameter of about 10~40nm of the nano-pore.
10. according to the moisture film of any one of foregoing item, wherein the aquaporin passage is deposited on the porous carrier Material is near or within.
11. a kind of moisture film, it includes the sandwich with least two lipid monolayers, when it is combined into one pair During molecular layer, the sandwich includes functional aquaporin aquaporin, and at least two lipid monolayer is by extremely Few perme-able support layers separate.
12. according to the moisture film of item 11, wherein the carrier layer, which includes to be formed with the lipid monolayer, contacts surface Hydrophobic perforated material, and wherein described lipid bilayer is formed in the perforation of the hydrophobic perforated material.
13. according to the moisture film of item 12, wherein the hydrophobic material has equivalent to deionized water drop and the hydrophobic material The hydrophobic deg of at least 100 ° contact angles between material, wherein the measurement of the contact angle is carried out under 20 DEG C and atmospheric pressure.
14. according to the moisture film of item 12 or 13, wherein the hydrophobic material is Parafilm or polytetrafluoroethylene (PTFE).
15. according to the moisture film of any one of item 11~14, wherein the hydrophobic material is plane, and the perforation exists It is uniformly distributed in midplane between 2 surfaces of the hydrophobic material and the essentially all perforation all has basic phase Same geometry, such as the perforation that any one of item 37~40 is limited.
16. according to the moisture film of any one of item 11~15, wherein the diameter of the perforation with millimeter to micrometer range.
17. according to the moisture film of any one of item 11~16, wherein the lipid bilayer such as any one of item 2~5 institute Limit.
18. according to the moisture film of any one of foregoing item, wherein the aquaporin is AQP1, such as ox AQP1.
19. according to the moisture film of any one of item 1~14, wherein the aquaporin comes from plant, such as TIP, PIP or NIP aquaporins and its mixture and heterozygote.
20. according to the moisture film of any one of item 1~14, wherein the aquaporin aquaporin is selected from water-glycerol passage Albumen (GLpF), for example, GLPA passages, GLPB1 passages, GLPB2 passages, GLPB3 passages and GLPY2 passages and its mixture and Heterozygote.
21. according to the moisture film of any one of foregoing item, wherein the sandwich is further encapsulated in water permeability stabilization Change in film.
22. according to the moisture film of item 21, wherein the stabilized membrane is selected from silicone film, it is at a temperature of below about 50 DEG C With relatively small aperture.
23. according to the moisture film of item 21 or 22, it is also loaded into shell to provide a kind of water filtering device.
24. a kind of method for preparing moisture film, it comprises the following steps:
A) the lipid microcapsule bubble containing aquaporin aquaporin is obtained, the aquaporin aquaporin accounts for the micro-capsule At least 0.1%mol/mol of bubble,
B) by the Vesicle fusion into planar lipid bilayer, the planar lipid bilayer is located at hydrophilic On the substantially planar permeable carrier on surface, wherein the lipid bilayer of aquaporin covering at least 1% Area,
C) optionally repeat step b) to obtain the bilayer of multiple fusions,
D) the substantially planar permeable carrier for having water-wetted surface by second deposits to step b) or c) the middle institute obtained State on lipid bilayer, to obtain sandwich, and
E) optionally the sandwich of gained is encapsulated in permeability stabilized membrane.
25. a kind of method for preparing moisture film, it comprises the following steps:
A) the lipid microcapsule bubble containing aquaporin aquaporin is obtained, the aquaporin aquaporin accounts for the micro-capsule At least 0.1%mol/mol of bubble,
B) by the Vesicle fusion into planar lipid bilayer, the planar lipid bilayer is assembled in thin Around the substantially planar permeable carrier of water surface, wherein the bilayer of aquaporin covering at least 1% Area, and
C) optionally the sandwich of gained is enclosed in permeability stabilized membrane.
26. a kind of method for preparing ultra-pure water filtrate, it is included by the water film filtering water according to any one of item 1~23 Solution, to retain ion, particle, organic substance and colloid, thus the filtrate is to be substantially free of ion, particle, organic substance With the water of colloid.
27. a kind of reverse osmosis water filter being used for from saline source production desalted water, the desalted water can be used for irrigating Agricultural and/or replaced with as drinking water, wherein at least one final reverse osmosis filter membrane comprising functional aquaporin water The moisture film of passage.
28. a kind of reverse osmosis water filter being used for from thick water source production ultra-pure water, the ultra-pure water can be used for partly leading In body industry and/or pharmaceuticals industry, wherein at least one final reverse osmosis filter membrane is replaced with comprising functional aquaporin The moisture film of aquaporin.
29. a kind of reverse osmosis water filter being used for from thick water source production pure water, it is used for municipal water industry, chemistry Industry, drinking water indus, food industry, electronics industry, oil and gas industry, refining industry, pulp and paper industry, metal industry, Mining industry and power industry, wherein at least one final reverse osmosis filter membrane replaces with to be led to comprising functional aquaporin water The moisture film in road.
30. according to the water filtering device of any one of item 27~29, wherein applying osmotic pressure to the downstream of the moisture film.
31. according to the water filtering device of item 30, wherein the osmotic pressure is more than the dense molten of water source to be purified from osmotic pressure Liquid.
32. according to the water filtering device of any one of item 27~31, wherein described lead to comprising functional aquaporin water The moisture film in road is the moisture film according to any one of item 1~22.
33. a kind of be used for the water filtering device of extraction and recycle-water from body fluid such as urine, milk and sweat, it includes containing The moisture film of functional property aquaporin aquaporin, such as the moisture film according to any one of item 1~22.
34. a kind of method for being used to purify the water obtained from water source, methods described is included by appointing according in item 27~33 The water that the water filtering device filtering of one obtains from the water source.
A kind of 35. hydrophobic polymer film for including multiple perforation, wherein the perforation is uniformly distributed in the film simultaneously The essentially all perforation all has substantially the same geometry in midplane between 2 surfaces of the film.
36. according to the film of item 35, wherein each perforation be respectively provided be large enough to allow vapor by but it is small to foot With the aperture area for preventing aqueous water from passing through, such as 100nm2~1mm2The area of scope.
37. according to the film of item 35, wherein the greatest cross-section length of the perforation with millimeter~micrometer range.
38. according to the film of any one of item 35~37, wherein the film has the thickness of millimeter~micrometer range.
39. according to the film of any one of item 35~38, wherein the geometry of the perforation is selected from circular and ellipse.
40. according to the film of any one of item 35~39, wherein the perforation has essentially identical size.
41. according to the film of any one of item 35~40, wherein the film limited in such as item 13 it is hydrophobic Film, such as parafilm or poly tetrafluoroethylene.
42. a kind of film, it includes the sandwich with least two perme-able support layers, at least two permeability Carrier layer is separated by least one lipid bilayer comprising functional transmembrane proteins.
43. according to the film of item 42, it includes the feature that any one of item 2~9 is limited.
44. a kind of film, it includes the sandwich with least two lipid monolayers, when it is combined into one double points During sublayer, the sandwich includes functional transmembrane proteins, and at least two lipid monolayer is oozed by least one Permeability carrier layer separates.
45. according to the film of item 44, it includes the feature according to any one of item 12~17.

Claims (17)

1. for the reverse osmosis water filter from thick water source or saline source production purified water, wherein described device includes film, Functional aquaporin passage or water-glycerol channel protein passage recombinate in lipid vesicle and are converted into propping up in the film Hold layer, to form water filtration film, hydrone present in the thick water source or saline source may pass through the water filtration film so as to Produce purified water;The supporting course has hydrophilic film surface, and the supporting course includes the material selected from mica or polymer.
2. reverse osmosis water filter according to claim 1, wherein the aquaporin passage is plant origin.
3. reverse osmosis water filter according to claim 2, wherein the aquaporin passage of the plant origin is selected from TIP, PIP or NIP aquaporin and its mixture and heterozygote.
4. reverse osmosis water filter according to claim 1, wherein the film includes water-glycerol channel protein passage.
5. reverse osmosis water filter according to claim 1, wherein the aquaporin passage be selected from GLPA passages, GLPB1 passages, GLPB2 passages, GLPB3 passages and GLPY2 passages and its mixture and heterozygote.
6. according to the reverse osmosis water filter in claim 1, wherein the aquaporin passage or the water-glycerol Channel protein passage is mutant protein.
7. reverse osmosis water filter according to claim 1, wherein the mica is mica tape.
8. reverse osmosis water filter according to claim 1, wherein the polymer is polysulfones or cellulose.
9. according to the reverse osmosis water filter of any one of claim 1-5,7 or 8, wherein the membrane closure is stabilized In porous or osmotic membranes.
10. reverse osmosis water filter as claimed in one of claims 1-8, wherein described device include multiple films to provide Multi-layer filtrating equipment.
11. it is used to extract from hydrous matter or solution according to the reverse osmosis water filter of any one of claim 1 to 10 The purposes of water.
12. purposes according to claim 11, wherein obtaining the molten of the increase concentration being dissolved in the hydrous matter or solution Matter.
13. a kind of method for preparing ultra-pure water filtrate, it is included by the reverse osmosis water according to any one of claim 1 to 10 Filter filtering solution, to retain ion, particle, organic substance and colloid, thus filtrate for be substantially free of ion, The water of grain, organic substance and colloid.
14. method according to claim 13, wherein, the reverse osmosis water filter includes the water as osmosis filtration film Film, osmotic pressure is applied to the downstream of the moisture film.
15. method according to claim 14, wherein the osmotic pressure applied to the downstream of the moisture film is more than water source to be purified Osmotic pressure.
16. according to any one of claim 13-15 method, wherein methods described is used for extraction and recycle-water from body fluid.
17. method according to claim 16, wherein the body fluid is selected from urine, milk and sweat.
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