CN104906962A - Membrane for filtering of water - Google Patents

Membrane for filtering of water Download PDF

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Publication number
CN104906962A
CN104906962A CN201510160535.XA CN201510160535A CN104906962A CN 104906962 A CN104906962 A CN 104906962A CN 201510160535 A CN201510160535 A CN 201510160535A CN 104906962 A CN104906962 A CN 104906962A
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water
film
aquaporin
reverse osmosis
passage
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CN104906962B (en
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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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Aquaporin AS
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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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Abstract

Disclosed are novel water membranes comprising lipid bilayers incorporating functional aqua- porins. The lipid bilayers are arranged in sandwich structures including hydrophilic or hydro not phobic support materials. Also disclosed are water purification devices/systems, including reverse osmosis filtering devices that include membranes having functional aquaporins. Methods of water purification and methods of preparing the membranes are also disclosed. Further, the invention provides for a new type of perforated, hydrophobic polymer film and to membranes containing lipid bilayers having other transmembrane proteins than aquaporins introduced.

Description

For the film of filtered water
The application is the divisional application of Chinese patent application CN201110008858.9, and the latter is the divisional application of Chinese patent application CN200680017301.9, and original application corresponds to international application no PCT/DK2006/000278.
Technical field
The present invention relates to a kind of new membrane, it comprises functional aquaporin (aquaporin) passage or the tetramer that are suitable for filtering pure water and/or glycerine, comprise the filter/purification system of this film, and utilize its method of producing ultra-pure water and extracting excessive water from Aquo-composition.The invention still further relates to novel hydrophobic polymer film.
Background technology
The various water treatment system for purifying natural water source and contaminated water source and method are developed traditionally, to obtain the purified water being suitable for people and/or animal edible.And semiconductor and pharmaceuticals industry have very high demand to ultra-pure water.The filter that the production requirement of ultra-pure water is more professional and the chemical treatment to water source.Employ multiple technologies, such as membrane filtration, ion-exchange, submicron particle filter or nanofilter, ultraviolet light and ozone treatment etc.The water produced very pure and only containing zero to the salt of unusual low concentration, organic principle, dissolved gases such as oxygen, suspended solid and microorganism such as virus and bacterium.But, due to the factor of the continued miniaturization in such as semi-conductor industry, make the specification of ultra-pure water become increasingly stringent.
Traditionally, water is designed for public by various and used point (point-of-use) the available water treating apparatus applied to come purifying or process, such as, based on following technology: activated carbon organic matter removal; Ultraviolet disinfection; Ion-exchange is except hardness (demineralized water), and film desalination such as counter-infiltration (RO) or nanofiltration (NF).But in water-treatment technology field, nanofiltration is relatively new.NF film produces soft water by being trapped in water the divalent ion producing hardness.NF film allows the monovalent ion such as sodium and chlorine of high percent to pass through, and it retains the divalent ion of high percent simultaneously.Because monovalent ion produces osmotic pressure, so water is pumped across RO film to high pressure in needing.Therefore, the pressure that water is pumped across needed for film by nano-filtration membrane is much smaller, this is because hydraulic drives power need not overcome the osmotic pressure from monovalent ion.Generally speaking, RO film for house and business water treatment applications removes whole dissolved solids of about 98%, and nano-filtration membrane removes the divalent ion (hardness components: calcium and magnesium) of about 90% and the monovalent ion (sodium chloride) of about 50%.
The desalter of membrane component (such as RO or NF) is used always to produce two strands of current when water leaves this element: desalination product water (it is through film) and effluent brine (it has flow through film surface).These abraum salt current must wash away salt on film and mineral matter, to prevent it in the Cumulate Sum fouling of film surface.If recur the accumulation of salt and mineral in the feedwater of film, then the material dissolved can precipitate and form solid film, makes film surface scale.In addition, colloid and particulate pollutant also can adhere to film surface and cause fouling.Owing to there is many aquatic pollutants, if therefore film irreversibly fouling or incrustation, then film can not be cleaned and must change.This characteristic of embrane method is especially reducing the serious problems in waste discharge for using point (POU) water treatment system to bring, and uses some water treatment system usually compact and builds economical as far as possible.
Ion interchange unit is also for softening so-called " hard water ".The problem of ion-exchange water softening system is that it is by removing hardness of water composition (calcium and magnesium ion) with sodium ion exchange, thus produces so-called " soft water ".When carrying out Ion Exchange Medium regeneration, the current of the sodium of high concentration, chlorine, calcium and magnesium ion enter sewerage system, produce environmental waste process problem.The example of this water purification system is recorded in the U.S. Patent No. 5 being entitled as " water purificationsystem having plural pairs of filters and an ozone contactchamber ", 741, in 416, it discloses a kind of water purification system, its efficient oxidation organic pollution and eliminate most of bacteriums in these current, virus and other microorganism.Relate to that to have optionally dialysis membrane system to monovalent cation also open in WO2004/099088.
Therefore, exist to for general family object and for advanced person's research, industry and pharmacy object process by or the lasting demand of the water purification system of water that may be polluted by chemistry, biological and/or radioactive pollutant.
Because water pollutions or water pollutions threaten the feature usually with height local, such as, on boats and ships or in remote mountain village or campsite, therefore need the fixing or portable water purification system that can be deployed in rapidly and easily reality or potential pollution place.Especially relevant is effectively can remove the pollutant in the water source of the reality such as such as seawater or potential pollution, to produce the process water that applicable people drinks.
Owing to having found to pass with selective conveying hydrone the Spinal Cord Oedema albumen aquaporin (aquaporin) that biomembranous ability is feature, there is certain interest in artificial moisture film design being introduced to these albumen, see U.S. Patent application No.20040049230 " Biomimetic membranes ", it relates to description and how to embed in film Spinal Cord Oedema albumen to realize the purifying of water.Described preferred form has conventional filter disc form.In order to manufacture this dish, LB groove (Langmuir-Blodgett trough) is utilized the monolayer of synthesis triblock copolymer thick for 5nm and protein to be deposited on the commercial ultrafiltration dish of 25mm.Subsequently, utilize this polymer of UV-irradiation and make the monolayer on dish crosslinked to improve its durability.This device can make pressurized water source pass in the room of film to test by being arranged on.But, not about how selecting the guidance of synthesizing triblock copolymer, the supported data of the aquaporin actual functional capability yet do not embedded.
Propose to innovate desalt technology on porous support by aquaporin being expressed as lipid bilayer vesica and being cast by these films, see James R.Swartz, homepage https:// chemenq.stanford.edu/01About the department/03Faculty/Swartz/swartz.html.
Main purpose of the present invention is to develop a kind of the water for industrial use filter membrane and the device that comprise the aquaporin introduced in film, and it can the water of purifying highest purity, and such as 100%.Do not have known technology or filter can complete this task at present.
Summary of the invention
On the one hand, the present invention relates to a kind of film for filtered water, the utilization of this film is recombinated and is converted the Spinal Cord Oedema albumen aquaporin (aquaporin) of supporting course in lipid vesicle, forms water filtration film in order to by such as Langmuir-Blodgett method.
The advantage of moisture film of the present invention comprises: effective desalination of seawater (earth water of 97-98% is seawater), and do not need desalination chemicals and the portable desalination filter device of Separation of Water and salt (one is similar to " coffee strainer " can) is provided, for the High-efficient Water purifying of semi-conductor industry, durable domestic water/drinking water purifying and non-electric desalt, such as, for third world countries.
Therefore, on the one hand, the present invention relates to a kind of moisture film, it comprises the sandwich that at least one that have at least two perme-able support layers and separate described perme-able support layers comprises the lipid bilayer of functional aquaporin aquaporin.Like this, permission hydrone is arrived at least one lipid bilayer be deposited between carrier layer by this permeability or porous carrier through carrier.Then, comprise a lipid bilayer filtered water of the functional aquaporin passage of dispersion, or also filter glycerine when aquaporin is GLpF passage, make it arrive the porous carrier layer of offside, produce the filtrate be made up of pure water.The water of preferred this filtration is ultra-pure water (UPW), and it is the highly purified water that ion, particle, organic matter and colloidal content are low.Moisture film of the present invention represents the reverse osmosis membrane of new generation utilizing known most optionally water carrying channel.
In this article, " moisture film " refers to and a kind ofly allows water to pass through and the structure that simultaneously do not allow that other material of great majority or material pass through.Preferred moisture film of the present invention is basic only through water (through glycerine under certain situation), and mustn't pass through with other solvent by solute.
A second aspect of the present invention relates to a kind of moisture film, it comprises the sandwich with at least two fat monolayers, when it is combined into a bilayer, described sandwich comprises functional aquaporin aquaporin, and described at least two fat monolayers are separated by least one perme-able support layers.In this embodiment, when carrier layer comprises perforation, two fat monolayers that this perme-able support layers can form lipid bilayer separate.
Another aspect of the present invention relates to a kind of water filtering device, and it comprises moisture film of the present invention, is optionally sealed in the stabilized membrane be installed in shell, and described shell has the entrance for aqueous fluid to be purified and the outlet for purified water.
The invention still further relates to a kind of method preparing moisture film, it comprises the following steps:
A) obtain the lipid microcapsule bubble comprising aquaporin aquaporin, described aquaporin aquaporin accounts at least 0.1%mol/mol of described microcapsule bubble,
B) by described Vesicle fusion in planar lipid bilayer, described lipid bilayer is positioned at and has the basic on the permeable carrier of plane of hydrophilic surface, and wherein the albumen of aquaporin covers the lipid bilayer layer region of at least 1%,
C) optional repetition step b) to obtain the bilayer of multiple fusion,
D) basic second permeable carrier for plane with hydrophilic surface is deposited to step b) or c) on the lipid bilayer that obtains, to obtain sandwich, and
E) optionally the sandwich of gained is enclosed in infiltrative stabilized membrane.
The invention still further relates to a kind of method preparing moisture film, it comprises the following steps:
A) obtain the lipid microvesicle bubble comprising aquaporin aquaporin, described aquaporin aquaporin accounts at least 0.1%mol/mol of described microcapsule bubble,
B) by described Vesicle fusion in planar lipid bilayer, described lipid bilayer is assembled in be had hydrophobic surface basic wherein said aquaporin covers the lipid bilayer layer region of at least 1% for around the permeable carrier of plane, and
C) optionally the sandwich of gained is enclosed in infiltrative stabilized membrane.
The invention still further relates to a kind of reverse osmosis water filter comprising moisture film (such as moisture film of the present invention) as osmosis filtration film, described moisture film comprises functional aquaporin aquaporin.
The invention still further relates to a kind of water filtering device for extraction and recycle-water in the body fluid from such as urine, milk and sweat, it comprises the moisture film containing functional aquaporin aquaporin.
In addition, the present invention relates to a kind of method preparing pure water, described pure water is obtained by natural with water film filtering of the present invention or contaminated water source.The feature of described pure water is the pollutant not having such as dissolved substance or particle.The invention still further relates to a kind of method obtaining purified water, it utilizes the reverse osmosis membrane comprising functional aquaporin passage to filter water source.
In addition, different aspect of the present invention relates to a kind of hydrophobic polymer film, and it will be described in more detail below.
Finally, the master-plan of moisture film of the present invention is also considered to the film being applicable to other purposes, is wherein otherwise designing in the film being used as moisture film of the present invention other transmembrane protein introduced beyond water removal channel albumen.These films are also parts of the present invention, and except the selection of transmembrane protein, these films are all identical with film disclosed herein in every respect, and all disclosures relating to these films all by after the amendment of necessity (mutatismutatndis) be applied to the film of other transmembrane protein beyond containing water removal channel albumen.
The transmembrane protein being different from aquaporin being applicable to membraned inclusions of the present invention is such as selected from but is not limited to any transmembrane protein in transport protein taxonomy database (TCDB).TCDB can be from https:// www.tcdb.orgenter.
The example comprising TCDB transmembrane protein is in the present invention:
Gas lysin passage forms toxin
Agrobacterium target host cell membrane anion channel
A-hemolysin channels forms toxin
Alamethicin passage
Alginate outlet opening albumen
Amoeba lysin
Amphiphilic peptide melittin
Amyloid b-protein peptides
Animal inward rectification K +passage
Annexin
Apoptosis regulators
ArpQ cave albumen
AS-48
ATP gating cationic channel
Automatic transport protein
Hay bacillus j 29 cave albumen
Bacterium class III target cell pore
Bacterium power/permeability increasing protein
Bacteriocin AS-48 ring type polypeptide
Bacteriorhodopsin
Beticolin passage
BlyA cave 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-endotoxin of passage
Form the leukocidin cytotoxin of passage
Chlamydia PFP
Chloride channel
The cationic channel formation of chloroplast membranes
The adventitia solute channel of chloroplaset
Mercaptan in conjunction with cholesterol activates cytolysin
Clostridium cytotoxin
Complement protein C9
Compound poly butyric ester-Ca 2+passage
Corynebacteria PFP
Cph1 cave 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 passage
The chloride channel of epithelium
The Na of epithelium +passage
FadL outer membrane protein
The Outer membrane protein of Fusobacterial
Form the connection albumen that gap connects
Form the innexin that gap connects
General bacterial porins
Glucose selective OprB PFP
The neurotransmitters receptor ion channel of glutamate gating
Gp91 phoxthe cyt b that macrophage NADPH-oxidizing ferment is relevant 558h +passage
GA passage
H +or Na +the bacterial flagellum motor of displacement
H +or Na +the bacterium MotAB Bacterial flagellar motor/ExbBD adventitia transport of displacement
Breathe out bit and belong to Outer membrane protein
HP1 cave albumen
Influenza matrix-2 passage
Insect defensin
Chloride channel in born of the same parents
J11 cave albumen
JAdh cave albumen
JU53 cave 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 cave albumen
LydA cave albumen
Magainin
Main intrinsic protein
Aptoxin bematolysis peptide
Metal-ions transportation albumen (passage)
Microcin E492
Mitochondria and plastid PFP
Mycobacterium PFP
Nisin
Non-selective cation channel-1
Non-selective cation channel-2
Form the Outer membrane protein of nucleosides specificity passage
OmpA-OmpF PFP
OmpG PFP
The chloride channel of organelle
The secretin of epicyte
Adventitia auxilin
The adventitia factor
Adventitia pilus connects and draws PFP
Outer membrane protein
Outer membrane receptor
P2 cave albumen TM
P21 cave Protein S
Football rhzomorph
Phospholemman
Pilosulin
Plant defensin
The plasmodesmus of plant
Plant thionine
Lactobacillin EF
Lactobacillin JK
The plastid peplos PFP of 16kDa
The plastid peplos PFP of 21kDa
The plastid peplos PFP of 24kDa
Polycysteine cationic channel
Polyglutamate ion channel
Pore-forming actinocongestin
Pore-forming hemolysin E
Pore-forming RTX toxin
PRD1 cave albumen M
The fragments of peptides of prion
The cell membrane of Pseudomanas cloves HrpZ target host
Pseudomonad OprP PFP
Gossypose PFP
Silk core PorCa PFP
Blue Buddhist nun's alkali-inositol-Isosorbide-5-Nitrae, the Ca of 5-tricresyl phosphate salt acceptor 2+passage
Saponin passage
Shiga toxin B-chain
Short-chain amides and urine PFP
Little conductance mechanical sense answers ion channels
Sugar PFP
Syringomycin passage
Syringopeptin channel
T4 cave albumen
T4 immunity cave albumen
T7 cave albumen
The anti-peptide bacterium of king crab
Tolaasin passage
For the TonB-ExbB-ExbD/TolA-TolQ-TolR of outer membrane receptor (OMR)-mediation-activator
Momentary type receptor potential Ca 2+passage
Three drastic crack hemolysin BL
Two-partner secretory pit albumen
Type B influenza virus NB passage
Urine transport protein (passage)
Urine/acid amides passage
Vacuolating cytotoxin
Vibrios chitoporin/Neisseria PFP
The ion channel Superfamily of voltage gating
The shaft-like prominent PFP of whipworm
Saccharomycete sterilization toxin K1
The cation selective Ca that yeast ext activates 2+passage
Other aspects of the present invention comprise use moisture film and extract excessive water from hydrous matters or solution, such as, obtain the expectation solute concentration of increase.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the various parts of the moisture film shown according to an embodiment of the invention, and this moisture film introduces the support lipid bilayer of aquaporin molecule in the sandwich example according to moisture film of the present invention having.
Fig. 2 is the schematic diagram of the various parts of the moisture film shown according to an embodiment of the invention, this moisture film has according to the support lipid bilayer introducing aquaporin molecule in the sandwich example of moisture film of the present invention, and the lipid bilayer wherein comprising aquaporin passage is positioned at the hole of permeability or porous carrier materials.
Fig. 3 is the schematic diagram describing the Biomimetic membranes design comprising aquaporin.This figure shows the various parts of film according to another embodiment of the invention, and this film has the support lipid bilayer introducing aquaporin, and described aquaporin is clipped in around voided polytetrafluoroethylene film.
Fig. 4 is the schematic diagram describing the Biomimetic membranes design comprising aquaporin.This figure shows the various parts of film according to another embodiment of the invention, and this film has the support lipid bilayer introducing aquaporin, and described aquaporin is clipped in around voided polytetrafluoroethylene film and is also encapsulated in further in sandwich.
Fig. 5 is the schematic diagram of the various parts of a kind of moisture film of display, and described moisture film comprises the encapsulating sandwich lipid bilayer introducing aquaporin.
Fig. 6 is the schematic diagram of encapsulating moisture film of the present invention, and now described moisture film is arranged on having in the filter housing of entrance and exit according to another embodiment of the invention.
Fig. 7 is the schematic diagram of display according to each assembly of the water purification system of another embodiment of the present invention.This system comprises following assemblies: thick water inlet, two media filtration room, water softener room, wherein optionally add bisulfites and escharotic, reverse osmosis filter 1 and 2 (RO1, RO2), its storage tank being connected to the pump in the loop by RO1 and RO2 filter had for additional purification, exhaust outlet and there is UV disinfection room.
Fig. 8 illustrates the aquaporin of protein and each member of water-glycerol channel protein groups.
Fig. 9 is the atomic force microscopy of the film formed on mica.This film is according to the program preparation described in embodiment 1.
Figure 10 shows a kind of filter comprising spiral winding moisture film of the present invention.
Figure 11 is the cross-sectional view strength intercepted along the line II-II of Figure 10.
Figure 12 is the schematic diagram illustrated by supporting bilayer from the preparation of air-water interface LB deposition of lipids.The left side shows the deposition of the first monolayer, the deposition of the right display second layer.
Figure 13 is the schematic diagram that Vesicle fusion program is shown.Vesica to be adsorbed onto on substrate and to break to form support bilayer.
Figure 14 illustrates the schematic diagram being supported lipid bilayer by spin-coating method preparation.
Detailed description of the invention
Living cells close by bimolecular lamellar lipid membrane, and to separate with other cell and extracellular matrix thereof.Bimolecular lamellar lipid membrane is impermeable water, ion and other polar molecule substantially; But in many cases, these entities are usually because response born of the same parents are outer or intracellular signal and needing by fast and optionally transmembrane transport.Spinal Cord Oedema task is completed by aquaporin (Preston et al., 1992).Aquaporin is all most important to any type of life, and is all being found in all organisms of people from bacterium through plant.Aquaporin promotes that water transport that is quick and high selectivity is defeated, thus allows cell to regulate its volume and inner osmotic pressure according to the differential static pressure of cell membrane both sides and/or permeable pressure head.In human body, the physiological significance of aquaporin is perhaps remarkable in kidney, and in kidney, every day needs from crude urine, reuptake ~ 150-200 premium on currency, and the water transport namely activating aquaporin promotion when water must reclaim rapidly from body fluid is defeated.In kidney, mainly through two kinds, this may be called that the aquaporin (having the aquaporin that 11 kinds different in known human body) of AQP1 and AQP2 realizes.In plant, aquaporin absorbs for the water of root and maintains water balance in plant also most important (Agre et al., 1998, Borgnia et al., 1999).Various organism and in-house water transportation research show, aquaporin has slot, and it prevents any large molecule, ion (salt) even proton (H 3o +) and hydroxide ion (OH -) flow through, maintain high water permeation speed simultaneously; ~ 10 9molecule H 2the every passage of O (Agre et al., 1998, Borgnia et al., 1999) per second.Until 2000 and calendar year 2001 (Fu et al., 2000 when having reported the bacterium channel protein water-glycerol channel Protein G IpF of first high accuracy 3D structure of AQP1 and relevant transmission glycerine; Murata et al., 2000; Ren et al., 2001; Sui et al., 2001), also know little about it about the reason of water selective.
But based on experimental configuration, propose detailed computer model, it not only explains Thief zone speed and strict water selective, and explain ability (de Groot and Grubm ü ller, 2001 that aquaporin prevents proton seepage; 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 fact, the structure of aquaporin allows hydrone only to pass through with single file, and selective to any charge species of the electrostatic regulable control aquaporin of channel interior, namely transport (de Groot andGrub-m ü ller, 2001 of any salt (ion) and proton and hydroxide ion are cancelled; 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 brief, this means the water hole only having hydrone by aquaporin, other not by.
Each shipped ~ 10 in the passage of aquaporin 9h 2o molecule/second, namely ~ 4 × 10 9molecule/passage/second.Therefore, 1g aquaporin can transport ~ 720 premium on currency/second under extra-high voltage.The water obtained by the Channel filtration of functional aquaporin is ~ 100% pure water, not containing ion, particle, organic matter and colloid, such as by ~ 100% H 2o forms.
The aquaporin race of memebrane protein as used herein also comprises GLpF albumen, and except hydrone, it is also glycerol channel.Preferred aquaporin has plant origin, such as TIP, PIP or NIP aquaporin, see Fig. 8.
Hereafter disclosed film of the present invention will only by water, thus promote the purifying of water, desalination and molecular concentration by counter-infiltration.Known water channel protein refusal, by all pollutants, comprise bacterium, virus, mineral, albumen, DNA, salt, washing agent, dissolved gases and the proton even in the aqueous solution, but due to its structure, aquaporin can transport of water.In addition, relevant water-glycerol channel albumen (GLpF) family can transport glycerine.Each aquaporin comprises NPA (asparagine-Pro-Ala) ring protein anchor being fixed on cross-film alpha helical region in film and two high conservatives, and described ring connects at the culminating point opposite vertexes of protein, forms a kind of hourglass shape.Verified, the motion of water is symmetrical, and can advance along any direction; This fact is very important, because this process not consumed energy.Due to hydraulic pressure or osmotic pressure, water passes film along specific direction.
Therefore, never drinkable water source can obtain pure water, if or source water contain interested chemical substance, then optionally can dewater, in input room, leave the expectation chemical substance of high concentration.But importantly, for except its to water exclusive selective except other reason, aquaporin is also applicable to the present invention.Many members of this protein families can bear the harsh conditions of Polluted Source Water and not loss of function.Aquaporin can be resisted owing to being exposed to the sex change or unfolding that acid, voltage, washing agent and heat causes.Therefore, film of the present invention can be used for purifying may be blocked or be damaged the source water of the chemical contamination of other film, and it can be used in the region continuing experience high temperature.
Aquaporin also can suddenly change.Because protein can be specific expressed in host bacteria according to the gene order affecting its net shape and function, so technical staff can change its genetic code easily, to change the proterties of protein.Therefore, protein can be designed as the expectation application performing and be different from protein Elementary Function.Such as, change into cysteine only by by the particular amino acid residue near aquaporin central authorities, the aquaporin produced will any free mercury in binding soln, and stop the transport of water due to obstruction.Therefore, these muteins used in film device can too high by toxic substance concentration time simply stop the mercury pollution that detects in water sample of flowing.
Finally, the new membrane of producing based on protein is also very cheap.The lipid microcapsule bubble comprising the cell membrane fragments with the AQP1 being derived from ox red blood cell is cheap aquaporin source.
As selection, aquaporin can obtain with the amount of milligram level from engineering dust Xi Shi Escherichia coli (E.coli) bacterial strain.According to estimates, the pure protein of about 2.5mg can be obtained from its often liter of culture of production, see U.S. Patent application No.20040049230.
Therefore, we this openly utilize biology assembly from fouling, saliferous or realize the method and apparatus of the complete pure water of High-efficient Production water that alternate manner pollutes.The present invention proves the integrated of the defeated bioprotein of water transport and external device (ED), and point out can the production ways of large-scale production water purifying device.
a first aspect of the present invention
In above-mentioned first aspect of the present invention, moisture film has sandwich, at least one lipid bilayer comprising the aquaporin of functional aquaporin of at least two perme-able support layers described in described sandwich has at least two perme-able support layers and separates.
Therefore, the moisture film of first aspect present invention is made up of amphipathic lipid plasma membrane, such as, comprise the film of the lipid described by table 1.Therefore, lipid bilayer substantially by be selected from phosphatide, phosphoglyceride, sphingolipid and cuorin and composition thereof amphiphilic lipids form, the phosphatide such as such as 1,2-bis-palmityl-sn-phosphatid ylcholine (DPPC), or the mixture of phosphatide.
As selection, lipid bilayer substantially can be made up of polymerizable lipid or contain polymerizable lipid, see table 1.
Therefore, moisture film of the present invention comprises the aquaporin of the restructuring aquaporin on porous carrier.Be preferably selected from for the preparation of the useful carrier material with water-wetted surface according to moisture film of the present invention: mica is as muscovite, mica tape, polysulfones, AlO 2such as there is the polymeric material of water-wetted surface as cellulose.Carrier material is plane substantially, this means that this carrier is preferably smooth, but allows carrier to have curvature, such as required during manufacture spiral winding filter curvature.In this case, carrier material is preferably flexible material, such as cellulose membrane.
This porous carrier preferably comprises the materials such as such as mica, and it has the structure of the basic plane comprising water-wetted surface, and wherein such as forms micropore or nano-pore by etching.Therefore, in the embodiment of first aspect, it is the hydrophilic layer that millimeter arrives the micron-sized basic plane containing mica or mica tape that perme-able support layers comprises thickness, and is wherein formed with the nano-pore (such as by etching as track-etch technique formation) that diameter is less than about 50 nanometers (usually in the scope of 10 ~ 40 nanometers).Mica is preferably muscovite.
This perme-able support layers also can comprise hydrophilic film surface, such as, be selected from silicone film, polysulfones, AlO 2such as celluloses etc. have the film of the polymer of water-wetted surface, are wherein formed with the nano-pore that diameter is less than about 50 nanometers (usually in the scope of 10 ~ 40 nanometers).
Lipid film containing aquaporin can be the bilayer being similar to biological cell membrane natural structure, or this lipid film can be made up of the bilayer of the lipid vesicle of multiple fused deposition.Described lipid preferably has amphiphilic, such as phosphatide (or phosphoglyceride), sphingolipid and cuorin.When being deposited on porous substrates by lipid layer, the passage of aquaporin can be preferably deposited near the hole that is pre-existing in carrier material or in hole.
Permeability used in the preferred embodiments of the invention or porous carrier are preferably according to R.M.Webber, J.L Anderson, and prepared by M.S.John, Macromolecules 23 (1990), 1026-1034, wherein record:
" film is made up by track-etch technique of the isinglass of about 7 nanometer thickness.For trace-etching-film, form hole by etching with hydrofluoric acid solution the track produced by the collimation fission fragment in californium 252 source.The time that the quantity in hole is exposed to fission source by film controlled, and the radius in hole is determined by the concentration of etching period, temperature and hydrofluoric acid water-bath.The size uniform of this some holes, and perpendicular to the surface of film.The uniformity in aperture is a key character of these films, because significant pore-size distribution is by owing to causing the indefinite consequence of polymeric layer hydraulics thickness by the bias current of macropore.The area of section mark in the hole of the illuminated part of film is about 1%; Therefore, the single hole sum of being simulated by binomial pore-size distribution is greater than 96%.Because hole is perpendicular to the surface of film, so the length in hole (1) equals thickness; This thickness is determined from known film size and weight.”
The quantity of aquaporin and the final amt in the roughly equal hole that distributes and distribution in preferred acquisition and lipid layer.
a second aspect of the present invention
Also can recombinate in planar lipid bilayer the aquaporin of aquaporin, described lipid bilayer is assembled in around the porous carrier film with hydrophobic surface of such as poly tetrafluoroethylene, and wherein lipid monolayer is assembled in the both sides of porous carrier film.In the hole of porous carrier film, lipid bilayer will be assembled in the place of the aquaporin of aquaporin of can recombinating.
Therefore, a second aspect of the present invention is made up of the moisture film comprising the sandwich with at least two lipid monolayer, when described lipid monolayer is assembled into a bilayer, described moisture film comprises the aquaporin of functional aquaporin, and described at least two lipid monolayer are separated by least one perme-able support layers.Normally, carrier layer comprises the hydrophobic porous material forming contact surface with lipid monolayer, and wherein lipid bilayer is formed in the hole of hydrophobic porous material.
Preferred hydrophobic material has the hydrophobicity being equivalent at least 100 ° of contact angles between deionized water drop and hydrophobic material, wherein the measurement of contact angle is carried out under 20 DEG C and atmospheric pressure, such as, but preferably the hydrophobicity of higher degree, is equivalent to the hydrophobic deg of at least 105 °, 110 °, 120 ° and 120 ° contact angles.Preferred hydrophobic material is parafilm or polytetrafluoroethylene (PTFE).
Hydrophobic material is generally (but can be flexible and therefore flexible) of plane, and is uniformly distributed in the midplane of perforation usually between 2 planes of hydrophobic material and all perforation have substantially identical geometry substantially; Details about the perforation of hydrophobic material will provide hereinafter.
" midplane (intermediate plane) " is defined as the plane be made up of the point equal to the vertical range on arbitrary surface in planar hydrophobic material 2 surfaces.
The size of hydrophobic material middle punch should only be guaranteed can form stable amphiphilic lipids bilayer in perforation, makes them can have nanometer, micron or millimetre-sized size.
The ratio that hydrophobic material is preferably perforated between the perforation of material and not perforated area is maximum, because this is the lipid bilayer with aquaporin provide maximum area to realize the transport of water.The distance between each perforation is by the importance of the pattern formed of boring a hole.Optimum pattern is hexagonal perforation pattern, has minimum " wall thickness " in this pattern between each perforation.But, prove that square pattern also can be enough.
Therefore, the moisture film of second aspect present invention is also made up of amphipathic lipid plasma membrane, such as, comprise the film of the lipid described in table 1.Therefore, lipid bilayer substantially by be selected from phosphatide, phosphoglyceride, sphingolipid and cuorin and composition thereof amphiphilic lipids form, the mixture of the phosphatide such as such as 1,2-bis-palmityl-sn-phosphatid ylcholine (DPPC) or phosphatide.Mainly be that this film only forms bilayer at the region place that hydrophobic carrier is bored a hole with the difference of first aspect, and lipid is organized as hydrophobic carrier faced by its hydrophobic side and aqueous environment faced by its water-wet side.
the preparation of bilayer
The intrinsic permeability of membrane material must be guaranteed.The material with hypotonicity will by preferably, but it must be firm and can introduce aquaporin to form the 2D filter array of monolithic stability and densification simultaneously.The various program of usual use prepares support lipid bilayer.Simple technology is LB method.Lipid soln in suitable organic solvent to be spread in the water parfacies in Langmuir groove and evaporation of organic solvent.A pair moveable barrier sheet is used from the side lipid film to be compressed to the surface pressing of expectation.Then substrate is passed perpendicularly through film, thus lipid layer (individual layer) thick for molecule is transferred to (see Figure 12) on substrate.Again the second monolayer can be shifted through film by making substrate.By vertical (Langmuir-Blodgett) deposition process transfer three monolayers altogether, but the 4th layer of level deposition method transfer that can utilize so-called Langmuir-Schaeffer (LS) is last one deck.These methods can use together with various lipid.Primary biomembrane is normally asymmetric.LB and LS both provides the possibility preparing asymmetric bilayer.This is realized by the lipid film exchanged between deposition in parfacies.
The another kind of mode that preparation supports bilayer is Vesicle fusion method (Brian andMcConnell 1984).The solution of little monolayer vesica (SUV) is applied to hydrophiling silicon chip or newly rives on the surface of mica sheet.When this sample is placed under low temperature (4 DEG C), vesica and surface are merged and are formed continuous print bilayer (Figure 13).Be not limited to any theory, supposed that first vesica is adsorbed onto substrate surface, then merge and form smooth pancake shape structure, finally break and launch, forming single bilayer (Reviakineand Brisson 2000) from the teeth outwards.Also propose after merging with substrate, only have the vesicle fraction of directly contact substrate to become and support bilayer (Leonenko et al.2000).By this mechanism, the edge that vesica has most higher curvature breaks, and the top of bilayer can move to the surface of substrate subsequently, to increase the size of formed support bilayer.Reported to be applied in on-chip a few minutes at solution and formed bilayer (Tokumasu et al.2003), but this short incubative time may produce incomplete bilayer.A few hours or Overnight incubation also have been reported (Reimhult et al.2003, Rinia et al.2000).
Can be used for preparing the third technology supporting bilayer is spin-coating method (Reimhultet al.2003, Simonsen and Bagatolli 2004).In spin-coating method, drop in a suitable solvent, and is placed on substrate by Lipid dissolution, then rotary substrate, and solvent evaporates and produces lipid coatings simultaneously.According to the concentration of lipid soln, spin-coating film is made up of one or more lipid bilayer.But once hydration, described multilayer is proved to be unstable, and a support bilayer is usually only had to be retained on the surface (Figure 14).This program simple and fast, and the lipid (DPPC) having utilized low melting point lipid (POPC) and had intermediate change temperature and the lipid with very high transition temperature (ceramide) complete.Such as, available lipid comprises phosphatide and amphiphilic lipids.
When also wanting to introduce peptides and proteins in support bilayer, Vesicle fusion technology is the most applicable, because other mentioned program relates to protein or peptide solubilising in organic solvent.Many memebrane proteins may sex change in organic solvent, if when the large functional areas that especially they comprise are exposed in the aqueous solution of film both sides.Therefore, preferably peptide or protein are inserted in vesica.Before formation vesica, many peptides and proteins such as aquaporin can be molten altogether in organic solvent together with lipid, is then applied on substrate by the vesica comprising peptide.This completes with multiple peptide, 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).Preferably by alternate manner, memebrane protein such as aquaporin is inserted in vesica.This strategy that Reconstitution of Membrane protein can be utilized to enter vesica completes, as the paper " Supported bilayers as models ofbiological membranes " of Danielle Keller introduced herein, in February, 2005, MEMPHYS-center forbiomembrane physics, Physics Department, University of SouthernDenmark and Dansih Polymer Centre description to the cytochrome c oxidase as model protein in the introduction of the chapter 4 41 ~ 45 pages of National Laboratory, Denmark.
The multiple-level stack of single 2D array is possible and may Worth Expecting.The final size of stacked array will depend on overall robustness and the intrinsic permeability of selected membrane material/film composition.The stacking protein that may depart from slightly embeds single bilayer and may be support the system at bilayer place.Then, the follow-up a series of vesica events of caving on support bilayer can provide multiple filtration cell arrangement, assuming that the prerequisite of vesica is recombinated by suitable aquaporin.Stacking cell arrangement is introduced stabilized membrane or stabilization of polymers matrix and sew up these individual units subsequently and will produce integral filter net eventually through self assembling process.
the common trait of each side of the present invention
Many features are that each side of the present invention has:
Useful aquaporin for the preparation of moisture film according to the present invention is: AQP1, TIP, PIP, NIP (see Fig. 8) and composition thereof and heterozygote.Especially the aquaporin of plant origin is expected, because its risk comprising the pollutant that such as pathogenic virus and prion etc. are pernicious to people significantly reduces.In addition, the aquaporin of plant is natural plant gene products, and can overexpression and production in plant.
Therefore, the aquaporin of aquaporin is preferably selected from water-glycerol channel albumen (GLpF), such as GLPA passage, GLPB1 passage, GLPB2 passage, GLPB3 passage and GLPY2 passage and composition thereof and heterozygote.
In the permeable membrane that moisture film of the present invention is preferably enclosed in stabilisation or perforated membrane, described film can be rigidity or flexibility, and can serve as the protection of moisture film and from aqueous fluid to be purified, remove the prefilter of coarse particulate matter.As selection or extraly, moisture film of the present invention can be deposited on filter disc and form water filter.
Be microporous silicon siloxane film to the useful materials of the optional stabilized membrane for closed moisture film of the present invention, its there is relatively little aperture and about room temperature or lower than the temperature of about 50 DEG C under solidify.
The useful lipid formed for aquaporin restructuring and lipid bilayer is: POPC, DPPC, ceramide (see table 1) and composition thereof.
Table 1 is the list of the useful lipid of the lipid bilayer adopted for the formation of moisture film of the present invention:
Lecithin:
1,2-dimyristoyl phosphatidyl choline (DMPC)
DPPC (DPPC)
1,2-distearyl acyl phospholipids 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
The anti-oleoyl of 1,2-bis-(elaidoyl) lecithin
The sub-oleoyl lecithin of 1,2-bis-
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-oleoyl lecithin (POPC)
The sub-oleoyl lecithin of 1-palmityl-2-
1-palmityl-2-arachidonic acid acyl group lecithin
1-palmityl-2-two dodecahexaene acyl group lecithin
1-stearyl-2-oleoyl lecithin (SOPC)
The sub-oleoyl lecithin of 1-stearyl-2-
1-stearyl-2-arachidonic acid acyl group lecithin
1-stearyl-2-two dodecahexaene acyl group lecithin
1-oleoyl-2-palmityl lecithin
1-oleoyl-2-stearyl lecithin
1,2-bis-or 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 phosphatidyl monoethanolamine (POPE)
The sub-oleolyl phosphatidyl monoethanolamine of 1 palmityl-2-
1-palmityl-2-arachidonic acid acylphosphatidyl ethanolamine
1-palmityl-2-two dodecahexaene acylphosphatidyl ethanolamine
1-stearyl-2-oleolyl phosphatidyl monoethanolamine (SOPE)
The sub-oleolyl phosphatidyl monoethanolamine of 1-stearyl-2-
1-stearyl-2-arachidonic acid acylphosphatidyl ethanolamine
1-stearyl-2-two dodecahexaene acylphosphatidyl ethanolamine
The anti-oleolyl phosphatidyl monoethanolamine of 1,2-bis-
The sub-oleolyl phosphatidyl monoethanolamine of 1,2-bis-
1,2-bis-linolenyl phosphatidyl-ethanolamine
1,2-bis-arachidonic acid acylphosphatidyl ethanolamine
1,2-bis-or 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 phosphatidyl glycerine (POPG)
The sub-oleolyl phosphatidyl glycerine of 1-palmityl-2-
1-palmityl-2-arachidonic acid acyl phospholipids acyl glycerine
1-palmityl-2-two dodecahexaene acyl phospholipids acyl glycerine
1-stearyl-2-oleolyl phosphatidyl glycerine (SOPG)
The sub-oleolyl phosphatidyl glycerine of 1-stearyl-2-
1-stearyl-2-arachidonic acid acyl phospholipids acyl glycerine
1-stearyl-2-two dodecahexaene acyl phospholipids acyl glycerine
Phosphatidylserine:
1-palmityl-2-oleolyl phosphatidyl Serine (POPS)
The sub-oleolyl phosphatidyl Serine of 1-palmityl-2-
1-palmityl-2-arachidonic acid acyl phospholipids acyl serine
1-palmityl-2-two dodecahexaene acyl phospholipids acyl serine
1-stearyl-2-oleolyl phosphatidyl Serine (SOPS)
The sub-oleolyl phosphatidyl Serine of 1-stearyl-2-
1-stearyl-2-arachidonic acid acyl phospholipids acyl serine
1-stearyl-2-two dodecahexaene acyl phospholipids acyl serine
1,2-bis-myristoyl phosphatidylserine (DMPS)
1,2-DPPS (DPPS)
1,2-DSPS (DSPS)
1,2-dioleoyl phosphatidylserine (DOPS)
1,2-bis-or two dodecahexaene acyl phospholipids acyl serine
1,2-bis-mustard acyl phospholipids acyl serine
Special lipid:
Cuorin
Bipolarity lipid
Natural lipid-soluble extract:
Egg yolk lecithin
OX-heart lecithin
Brain lecithin
Beef liver lecithin
Soybean lecithin
Dust Xi Shi 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-phosphocholine (DTPC)
1,2-bis--10,12-tricosadiynoyl-sn-glycero-3-phosphoethanolamine (DTPE)
1-palmityl-2,10,12-tricosadiynoyl-sn-glycero-3-phosphoethanolamine (PTPE)
(DC8,9PC [two (10, the 12-tricosadiynoyl)-sn-glycero-3-phosphocholine of 1,2-]
Two PhyPC [1,2-bis-phytane acyl group (phytanoyl)-sn-glycero-3-phosphocholine]
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 manufacture this dish, the immobilized artificial membrane bilayer comprising the protein of functional aquaporin is deposited in the commercial ultrafiltration panel surface of 25mm by LB groove.In a preferred embodiment of the invention, moisture film optionally together with conventional film spiral winding form the RO module of spiral winding, see Figure 10 and 11.
Filter disc is arranged on to be had in the confined chamber of entrance and exit, such as, be connected to the filter disc room at the water source with pump through pipe, and described pump makes the source water of pressurization through film and flows out from outlet.When the opposite side only having pure water to pass film, and pollute solute start to keep high concentration in room time, then think that this device possesses function.Must pressurize to contaminated solution, flow into overcome pure water the natural tendency had in the compartment of the room of more dissolved particles, thus overcome the osmotic pressure of water, 10psi is about for drinking water.The object of moisture film of the present invention is counter-infiltration and pure water is separated with pollution solute.This trend of system or osmotic pressure can represent with pound per square inch (psi).Such as, the osmotic pressure of seawater is 360 ~ 400psi.
Several method is had to can be used for allowing this device to bear the pressure of these types.A kind of method be add high concentration nontoxic and the solute of easily removing in new Water Room, to promote the normal osmotic pressure of cross-film when counter-infiltration also appears in the pressurization due to room.And pressure needed for counter-infiltration also can by using multilayer water channel protein film to reduce in the cascade of the room that is tightly connected comprising the pollutant that concentration reduces continuously.Synthesis pressure in often pair of room needed for purified water is a part for the necessary gross pressure of counter-infiltration.Therefore, each film only need bear little pressure, thus has larger chance and remain intact.Therefore, if the concentration difference between often pair of room only has 10%, instead of 100%, the above-mentioned high pressure of 10% is so only needed at purifying source, each junction water.Pure water is by continuous seepage in the final stage room of pressure and flow constant.
Aquaporin reverse osmosis membrane can only in one step purifying contain the water of several dissimilar pollutant.Traditional high purity systems needs several parts that can comprise water softener, carbon filter, ion-exchanger, UV or chemical disinfection, and arranges the dual channel reverse percolating filter of conbined usage, then could production purified water.This complex appts can not remove dissolved gases or be less than 150 daltonian materials as aquaporin film.In addition, all these parts need to safeguard.UV bulb needs to change and energy.Ion-exchanger needs chemical regeneration when saturated.Softening agent needs salt.Carbon and reverse osmosis cartridge must be changed when fouling.Finally, single step device is by the space that requires far below typical purification system and weight, and this advantage realizes by the portable unit comprising the moisture film of aquaporin of the present invention.
Aquaporin film is also faster than conventional system.The conventional high speed reverse osmosis units clean water can producing about 28.4 liters (7.5 gallons) per minute.Current research shows hydrone with the rate motion of 54 μm of ol/ seconds through the saturated lipid film (0.0177mm of aquaporin 2).(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 1.0m 2theoretical water channel protein reverse osmosis membrane per minutely can filter the pure water being up to 3295 liters.This speed is 116 times of normal purification devices.
Another aspect of the invention relates to a kind of water treatment system, it is in order to therefrom to remove chemistry, radioactivity, biology and/or particulate pollutant, this system comprises entrance and is arranged to the monoblock type shell connecting external water source, wherein be furnished with one or more water filter unit comprising moisture film of the present invention in this monoblock type shell, described moisture film is arranged for the treatment of the water from external water source to produce ultrapure current, and wherein this monoblock type shell comprises the outlet for therefrom discharging described ultra-pure water.The example of this treatment system is reverse-osmosis filtering device.
Such as, but moisture film of the present invention also can be replaced with other film comprising functional aquaporin, the film comprising aquaporin of instruction in US 2004/049230.Regardless of the definite character of film comprising aquaporin, believe this water treatment system described herein and filter for installation creative with the ability of himself.
Therefore, the present invention also comprises the reverse osmosis water filter for producing desalted water from saline source, described desalted water can be used for agricultural irrigation and/or drinking water, wherein at least one final reverse osmosis filter membrane has replaced with the moisture film comprising functional aquaporin aquaporin, such as film of the present invention.Similarly, the present invention also comprises the reverse osmosis water filter producing ultra-pure water from thick water source, described ultra-pure water can be used for semi-conductor industry and/or pharmaceuticals industry, and 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 still further relates to a kind of reverse osmosis water filter for producing pure water from the thick water source used for municipal water industry, chemical industry, drinking water indus, food industry, electronics industry, oil and gas industry, rendering industry, pulp and paper industry, metal industry, mining industry and power industry, wherein at least one final reverse osmosis filter membrane has replaced with this moisture film comprising functional aquaporin aquaporin.Usually, osmotic pressure is applied to the downstream of described moisture film to drive water flow.This osmotic pressure is greater than the concentrated solution at water source to be purified usually from osmotic pressure.
The invention still further relates to a kind of water filtering device for extraction and recycle-water from body fluid such as urine, milk and sweat, it comprises the moisture film of the aquaporin containing functional aquaporin, such as moisture film of the present invention.
Water purification system/filter of the present invention also can comprise the particle filtering module of moisture film device upstream, and it also therefrom removes at least part of particulate pollutant for pretreatment current.
The function of this particle filtering module is the burden alleviating downstream water filter, makes the current required pressure that fully flows lower, thus optimizes the energy consumption of whole system and improve its operational efficiency.
Particle filtering module preferably includes one or more filter element being selected from (a) hollow fiber membrane separator and (b) ultra-filtering element.Multiple hollow fiber membrane separator and ultra-filtering element can adopt over-over mode to use, and maximize to make the particle removal ability of this particle filtering module.
Filter element preferably includes slipstream well known in the art or cross-flow filtration device, to prevent the blocking of filtering surface.
In order to the vulnerability of this particle filtering module being reduced to the inefficacy of single filter, and in order to reduce single cleaning filtration and the system down time during safeguarding, this particle filtering module preferably includes multiple filter element be arranged in parallel, and wherein each element provides independently filtration path for current.
This particle filtering module is preferably adopted in preliminary filter upstream, such as it can have the porosity of about 10 μm to about 20 μm, to leach the bulky grain (such as solid particle, spore and bacterium) in current, and to extend the life-span of filter device therefor in downstream particulate filtering module.
This pollutant removal unit can comprise nanofiltration (NF) module for removing the ion in current or counter-infiltration (RO) module.RO module is conventional to be used for this object and to be proved to be effective.In addition, compared with RO module, nanofiltration needs lower pressure and less energy and water consumption.
Water treatment system of the present invention can also comprise the hydraulic pressure that handled water flows into wherein and store groove, to maintain uniform pressure in system and to provide substantially invariable water supply for the water consumption factory in downstream.
Water treatment system of the present invention can also comprise water quality monitoring module, it is monitored one or more continuously and indicates the variable of pending effluent quality (such as including but not limited to: cl concn, pH value, electrical conductivity, total organic carbon, dissolved oxygen, chemical oxygen consumption (COC), turbidity and radioactivity), the baseline value that these variablees and the observation in advance by these variablees measure is compared, identify the remarkable deviation with these baseline values, and produce the output signal of the described deviation of instruction.Automated sensor can be used for accurately measuring these variablees, and sampler can be used for the discrete water sample of conventional Christmas, and sample is separated with time frame when there is deviation by this permission.Then various routine analyzer can be implemented to this sample, to identify in water the pollutant causing this deviation.This water quality monitoring module can also be run to be switched on or switched off water treatment system as required, and/or warning authorities water quality does not meet predetermined drinking water quality standard.
Water treatment system of the present invention can be fixing or portable.Its preferably built and arrange be used for vehicle transport and deployment, may be used for make it distally supplying water.
System of the present invention can adopt mode that is parallel and/or series redundancy to configure various assembly, to improve the performance of system reliability and whole system.Also will recognize, system described herein and embodiment can adopt functional redundancy to realize the removal completely of water pollutant.
System/water filtering device can be used for purified water, and as mentioned above, the present invention also relates to the method preparing purified water really, and wherein said method comprises makes water by systems/devices of the present invention.The water of such acquisition such as will not contain ion, particle, organic matter and colloid, because these parts have been trapped in device substantially.
hydrophobic membrane of the present invention
As described in the above-mentioned disclosure of second aspect present invention, namely hydrophobic material is comprised in the middle support layer that moisture film can surround at lipid monolayer, can prepare the material of hydrophobic membrane form, this hydrophobic membrane comprises the equally distributed perforation with uniform shape and size.Believe that this hydrophobic membrane itself is creative.
Therefore, the invention still further relates to the hydrophobic polymer film comprising multiple perforation, wherein said perforation is evenly distributed in film, and in midplane between 2 planes of hydrophobic material substantially all perforation there is substantially identical geometry.When these perforation all have large must be enough to allow steam by but little be enough to the aperture area preventing aqueous water from passing through time, such as 100nm 2~ 1mm 2area time, this film will produce with such as the effect of material equivalence, namely this film can be breathed freely but waterproof.Believe that film of the present invention is better than such as material because perforation size and geometry be subject to good control.
Term " hydrophobic membrane " herein refers to the hydrophobic material of basic plane.This film is normally flexible, makes planar materials can obtain the form (if that is, material is wrapped around the shaft) of curved surface, thus makes this hydrophobic membrane be suitable as a part for the fabric in clothing and other flexible structure.
This perforation has the greatest cross-section length of nanometer to millimeter scope usually, such as micrometer range, and this film has the thickness of millimeter to micron usually.
Usually, the geometry of perforation is selected from circle and ellipse.When using laser equipment to introduce perforation in film, two kinds of shapes all easily obtain-such as, circular hole can utilize static laser beam to obtain, and film will provide oval or even bar-shaped hole relative to the motion (by moving film or laser beam) of laser beam between exposure period.In preferred embodiments, perforation all has substantially identical size.Membrane material is selected from the above-mentioned hydrophobic material relevant to the disclosure of second aspect present invention usually.
When describing of the present invention with reference to particular of the present invention, will be understood that many changes, amendment and embodiment are possible, therefore all these changes, amendment and embodiment will be understood within the spirit and scope of the present invention.The all reference papers quoted herein are all incorporated to herein by reference.
By following discloses content and claims, other side of the present invention, characteristic sum embodiment will be obvious more fully.
Embodiment 1
The restructuring of AQP-1 (proteoliposome) in DPPC lipid vesicle
Use follow procedure preparation according to moisture film of the present invention
1. the preparation (SUV) of little monolayer vesica
A. by dry DPPC lipid suspension in milli-Q water to obtain the concentration of 1.3 ~ 1.5mM.
B. suspension incubation hydration in 1 hour at 55 DEG C is obtained polymolecular layer vesica (MLV)
C. by MLV Solution extrusion is prepared SUV 12 times through the polycarbonate filter of two 100 nanometers
D. at 55 DEG C, SUV solution is preserved.
2.BioBeads tM the preparation of (polystyrene bead)
A. 4g BioBeads is about with milli-Q water washing tM5 times
B. by the BioBeads through washing tMsonication 1 hour under water suction
3. recombinate
A. the SUV solution of proper volume pipette is moved in eppendorf pipe
B. the Triton X-100 of 50 μ l 20% is added
C. 10 μ l AQP-1 (concentration 0.5mg/ml) of denatured form in phosphate buffer are added wherein, the method purifying that described AQP-1 describes according to Zeidel et al. (1992)
D. milli-Q water is added to final volume 200 μ l
E. at room temperature Incubation solution, and jolting 15 minutes
F. about 75mg is added in solution through the BioBeads of washing, then incubation jolting 30 ~ 45 minutes
G. this solution pipette is moved in clean Eppendorf pipe
H. step f ~ g 3 times (BioBeads of totally four times) is repeated
I. this lipid protein liquid solution is for subsequent use
Fig. 9 shows AFM (AFM) photo of DPPC film on muscovite, and shows the AQP-1 recombinated in DPPC film, and it shows the support bilayer completing recombination and gained vesica.As measurement image gained, the little loop configuration area in image is about 36nm 2.Protein surface area in this and lipid bilayer meets very much.On an average (images from 6 different sizes of three zoness of different), protein covers the surface of 48%, and lipid covers the surface of 52%.Assuming that lipid area is 0.5nm 2, then the lipid-protein ratio (LPR) calculated is 77.Support bilayer to be obtained by the proteoliposome Vesicle fusion that LPR is 50.
Embodiment 2
Porous muscovite forms lipid bilayer and other multiple bilayer of possibility, to obtain the moisture film as Fig. 1 schematically shows.
1. by white clouds master slice (about 1cm 2) rive with band
2. after riving, immediately 25 μ l proteoliposome solution in embodiment 1 are applied to mica surface.
3. by sample at room temperature (21 DEG C) incubation 10 minutes to form the bilayer merged.
4. after incubation, with milli-Q water washing sample 7 times, excessive in vesica to remove.
5. finally newly rive second muscovite is deposited on formed lipid bilayer.
Embodiment 3
The restructuring of AQP-1 in E.Coli lipid-soluble extract vesica
The whole lipid-soluble extract of E.coli in chloroform derives from Avanti Polar Lipids (Alabaster, AL).Solvent (chloroform, ethanol, methyl alcohol, decane) is all purchased from Sigma-Aldrich (St.Louis, MO).SM-2BioBeads is purchased from BioRadLaboratories (Hercules, CA).The ownership is ultrapure milli-Q water (18.2M Ω cm for middle water -1).Obtained by the Dr.Jan Enghild of University ofAarhus as the suspension of unfolded protein by the aquaporin-1 of the red blood cell purifying of ox.
Chloroform is evaporated from lipid soln, and by dry lipid 100mM KCl hydration 30 minutes at 55 DEG C.Agitating solution, and by making the polycarbonate filter of solution through two 100nm in Lipex extruder (Northern Lipids, Vancouver, CD) form little monolayer vesica (SUV) for 12 times.By add Triton X-100 (Sigma) to 1.25% (wt/vol) final solubility and add subsequently AQP-1 to lipid-protein ratio (LPR) be 1000: 1 obtain recombinate mixture.Proteoliposome is formed by removing washing agent.This can realize by being adsorbed onto on hydrophobic BioBeads (SM-2).Proteoliposome can use the same day or one day afterwards in preparation.Between experiment, solution is preserved at 4 DEG C.
Embodiment 4
The formation of plane bi-layer membrane and voltage clamp test: AQP-1 introduces in lipid bilayer and do not increase ionic conductance
The electromotive force V of bilayer (or cell membrane) is controlled the level that (or " clamping down on ") is being expected by voltage clamp.Method used herein measures the electromotive force of the bilayer that the spacer place between leap two aqueous solution is formed.The silver electrode scribbling AgCl is put in one chamber, and electrically compares this voltage and voltage to be maintained (being called domination voltage).Then clamp down on circuit by another electrode, electric current to be returned in another room.Even if in the face of infiltrative change, this feedback circuit also will maintain the level of expectation across bilayer electromotive force.The most important thing is, this device allows to measure the electric current I by remaining on across bilayer electromotive force needed for given voltage simultaneously.Therefore, how voltage clamp technology indicating film electromotive force affects transmembrane ion electric current.This impact represents with current-voltage (I/V) relation.
Plane bilayer is by E.coli (Avanti Polar Lipids, Alabaster, AL) n-decane solution (2.5%wt/vol) is formed through the hole (diameter 1.3mm) in Teflon spacer, two kinds of non-cushioned 0.1M KCl aqueous solution isolation that experimental day is prepared by described spacer.Test by completing bilayer I/V with the silver-colored line scribbling AgCl as the AxoPatch200 amplifier (Axon Instruments, Sunnyvale, CA) of electrode at 22 DEG C.Set up I/V agreement, and utilize Clampex 9.2 software (AxonInstruments, Sunnyvale, CA) to record data.This data separate ends of the earth Bessel filter (Bessel filter) (Frequency Devices, Haverhill, MA) LPF under the angular frequency of 500Hz (-3dB), and carrying out 16 AD conversion (DigiDatal332A, Axon Instruments, Sunnvale, CA) after be stored in PC (Dell Computer, Austin, Texas) in for analyze.Analyze data, and by ClampFit 9.2 (Axon Instruments, Sunnyvale, CA) and OriginPro 7.5 (OriginLab, Northhampton, MA) display.
The formation of bilayer is monitored with the stereoscope (Zeiss) being furnished with cold light source (IntraLux 5000, Volpi, CH).After lipidosis is in the hole of spacer, newton's diffraction color of lipid polymolecular layer fades away, and forms transparent " black " lipid film surrounded by thicker lipid/decane annulus after 10 minutes.This desalination is also reflected under zero potential IRMS across in the root mean square temporary transient change of bilayer electric current.Initial IRMS is about 1.6pA, then rises to the steady-state value of about 6pA, and this instruction defines stable bilayer.This bilayer diameter is about 1200 μm.After bilayer is formed, utilize stepping agreement to obtain across bilayer electric current, wherein electromotive force steps to+90mV with the increment of 10mV from-100mV.Each step continues 1000ms, is 1000ms between step.
After the vesica containing AQP-1 is added bimolecular layer forming liquid (2: 1vol/vol), AQP-1 is introduced in plane bilayer, obtains similar result.
AQP-1 introduces lipid bilayer and does not change gas current, but compared with the control, that it changes the time constant of the bilayer comprising AQP-1.For first approximation, a rear observation may be interpreted as the change of the effective dielectric constant of annulus and bilayer.This is possible, because compared with hydrocarbon materials, the dielectric constant that AQP-1 protein material is lower will cause time constant lower in both bilayer and annulus.
Embodiment 5
Osmotic gradient is tested: the AQP-1 introduced in lipid bilayer produces osmotic gradient, and the ion concentration causing hypotonic side not stirred in layer increases
After the lipid bilayer containing AQP-1 is formed, do not stir K in layer by measuring near film +the change of ion concentration observes the cross-film water flux that osmotic pressure drives.
According to the technology of Zeuthen, the OD capillary glass tube (Corning120F) of 1.2mm is used to manufacture two-tube K +electrode.
By adopting 12 BioLogic 1401+AD/DA interface (Biologic, Claix, France) DUO773 amplifier (WPI) record of PC (Dell Computer, Austin, TX) is connected to from two-tube electrode voltage.
Two-tube electrode is placed in rear (suitable) room of the 100mMKCl of the pH 7.2 cushioned containing useful 20mM tri-[methylol]-aminomethane hydrochloride (TRIS) (T3253, Sigma, St Louis, MO) and carries out record.Installing electrodes fixture, electrode is stretched into along in room relative to aqueous solution angle surperficial at 45 °, and utilizes hydraulic pressure narishige (David KnopfInstruments, Model 1207B) to handle, minimum step is 0.25 μm.The stereoscope monitoring that the formation of bilayer and the coarse positioning of electrode utilize 5.3 joints to describe, and start record at lipidosis after 10 ~ 20 minutes.The overall accuracy of bilayer electrode distance is adjusted to about ± 7 μm, and adjusts absolute distance by the significantly change of close contact bilayer rear electrode electromotive force.Across osmotic gradient the producing containing KCl solution induction in (instead) side before 4M urea (452042V, BDH, Poole, UK) by the pH 7.2 containing useful 20mMTRIS buffering of bilayer.
Observe, when existing across bilayer osmotic gradient, the lipid bilayer introducing AQP-1 brings out water flow.
With body K +concentration is compared, and when there is osmotic gradient, the AQP-1 introduced in lipid bilayer makes K +ion concentration adds about 8% in hypotonic side within the scope of bilayer 20 μm.
Film can bear the osmotic gradient of 4M.
Embodiment 6
Comprise the UPW system according to film of the present invention
Figure 10 and 11 display water purification system according to an embodiment of the invention.Figure 10 is the perspective section schematic diagram of element, and Figure 11 is the cross-sectional view strength cut along the line II-II of Figure 10.
This element has the hollow tube 1 being arranged in element center, and its surface is formed with several through hole 1a.Reverse osmosis membrane 2, permeate passageway film 3 and feed channel film 4 are wound around with the outer surface of mode described below around hollow tube 1.
Each reverse osmosis membrane 2 entirety has bag-shaped shape, and permeate passageway film 3 is disposed therein.Bag-shaped reverse osmosis membrane 2 is connected to the outer surface of hollow tube 1, and its opening 2a is enclosed in the through hole 1a formed in hollow tube 1 simultaneously, and the inside of reverse osmosis membrane 2 is communicated with through hole 1a with permeate passageway film 3.
Each feed channel film 4 is arranged between coupled reverse osmosis membrane 2, and is configured to allow liquid to be connected to the two ends of film and channel components through framing component 5 wherein, obtains helical structure thus.
Said elements is arranged in pressure vessel, and is suitable for supplying feeding liquid 6 from its one end (upstream side) under a predetermined.
When feeding liquid 6 flows along feed channel component 4, it suffers the reverse osmosis separation of reverse osmosis membrane 2, is separated into penetrating fluid and solute.Through reverse osmosis membrane 2 and the penetrating fluid with low solute concentration flows into through hole 1a collecting in hollow tube 1.Then penetrating fluid 6a is taken out from the downstream of element.
Feeding liquid not through reverse osmosis membrane 2 continues to flow to downstream along feed channel component 4.During flow, feeding liquid absorption is separated and stays the solute on film surface from feeding liquid, thus becomes the concentrate 6b with high solute concentration.
Have a key issue when executive component, namely element function reduces due to concentration polarization.
Concentration polarization is that the impurity comprised in a kind of scale forming matter such as feeding liquid makes the concentration of solute and scale forming matter in feeding liquid higher than the phenomenon on film surface with enriching pollutants on the surface of the reverse osmosis membrane 2 contacted with feed channel component 4.As a result, osmotic pressure raises.
When there is concentration polarization, the amount of penetrating fluid reduces, and the such as contamination precipitation such as gel and incrustation scale is on film surface.For this reason, reverse osmosis membrane can not develop its capacity, and the performance of element then reduces.
The generation of concentration polarization can be suppressed by feeding liquid turbulent flow on the surface of the film.Such as, more easily there is turbulent flow in the linear velocity being increased film feeding liquid on the surface by the feed channel component 4 utilizing thickness less, makes concentration polarization layer can be thinning.
But because feed channel component 4 has less thickness, the scale forming matter such as impurity and Institute of Micro-biology that make the passage limited by feed channel component 4 easily be fed in liquid block.As a result, element function reduces and the pressure loss in feeding liquid increases.In order to keep the quality and quantity of penetrating fluid, the operating pressure of feeding liquid needs to improve, and therefore must provide the high-pressure pump needing operation power and high-voltage tube, it causes liquid production cost to increase.
At least one reverse osmosis membrane is according to the moisture film comprising aquaporin and/or water-glycerol channel protein channel of the present invention.
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Following content corresponds to the original claims in original application:
1. a moisture film, it comprises the sandwich with at least two perme-able support layers, and described at least two perme-able support layers are separated by least one lipid bilayer comprising functional aquaporin aquaporin.
2. according to the moisture film of item 1, described lipid bilayer substantially by be selected from phosphatide, phosphoglyceride, sphingolipid and cuorin and composition thereof amphiphilic lipids form.
3., according to the moisture film of item 2, wherein said amphiphilic lipids is DPPC or other phosphatide or its mixture.
4., according to the moisture film of item 1, wherein said lipid bilayer is made up of polymerisable lipid substantially.
5. the moisture film any one of aforementioned item, wherein said perme-able support layers comprise basic plane containing mica or mica tape and thickness is millimeter arrives micron-sized hydrophilic layer, and be wherein formed with the nano-pore that diameter is less than about 50nm.
6., according to the moisture film of item 5, wherein said nano-pore is formed by track-etch technique.
7., according to the moisture film of item 5 or 6, wherein said mica is muscovite.
8. the moisture film any one of aforementioned item, wherein said perme-able support layers comprises hydrophilic film surface, such as, be selected from silicone film, polysulfones, AlO 2polymer such as cellulosic film with having water-wetted surface, is wherein formed with the nano-pore that diameter is less than about 50nm.
9. the moisture film any one of item 5 ~ 8, the diameter of wherein said nano-pore is about 10 ~ 40nm.
10. the moisture film any one of aforementioned item, it is neighbouring or inner that wherein said aquaporin passage is deposited on described porous carrier materials.
11. 1 kinds of moisture films, it comprises the sandwich with at least two lipid monolayer, when it is combined into a bilayer, described sandwich comprises functional aquaporin aquaporin, and described at least two lipid monolayer are separated by least one perme-able support layers.
12. according to the moisture film of item 11, and wherein said carrier layer comprises the hydrophobic perforated material forming contact surface with described lipid monolayer, and wherein said lipid bilayer is formed in the perforation of described hydrophobic perforated material.
13. according to the moisture film of item 12, and wherein said hydrophobic material has the hydrophobic deg being equivalent at least 100 ° of contact angles between deionized water drop and described hydrophobic material, and the measurement of wherein said contact angle is carried out under 20 DEG C and atmospheric pressure.
14. according to the moisture film of item 12 or 13, and wherein said hydrophobic material is Parafilm or polytetrafluoroethylene (PTFE).
15. moisture films any one of item 11 ~ 14, wherein said hydrophobic material is plane, and to be uniformly distributed in the midplane of described perforation between 2 surfaces of described hydrophobic material and all described perforation all have substantially identical geometry, the perforation such as limited any one of item 37 ~ 40 substantially.
16. moisture films any one of item 11 ~ 15, wherein said perforation has the diameter of millimeter to micrometer range.
17. moisture films any one of item 11 ~ 16, wherein said lipid bilayer any one of item 2 ~ 5 limit.
18. moisture films any one of aforementioned item, wherein said aquaporin is AQP1, such as ox AQP1.
19. moisture films any one of item 1 ~ 14, wherein said aquaporin from plant, such as TIP, PIP or NIP aquaporin and composition thereof and heterozygote.
20. moisture films any one of item 1 ~ 14, wherein said aquaporin aquaporin is selected from water-glycerol channel albumen (GLpF), such as GLPA passage, GLPB1 passage, GLPB2 passage, GLPB3 passage and GLPY2 passage and composition thereof and heterozygote.
21. moisture films any one of aforementioned item, wherein said sandwich is encapsulated in water permeability stabilized membrane further.
22. according to the moisture film of item 21, and wherein said stabilized membrane is selected from silicone film, and it has relatively little aperture at lower than the temperature of about 50 DEG C.
23. according to the moisture film of item 21 or 22, and it is also loaded in shell to provide a kind of water filtering device.
24. 1 kinds of methods preparing moisture film, it comprises the following steps:
A) lipid microcapsule obtained containing aquaporin aquaporin is steeped, and described aquaporin aquaporin accounts at least 0.1%mol/mol of described microcapsule bubble,
B) by described Vesicle fusion in planar lipid bilayer, described planar lipid bilayer is positioned on the permeable carrier of the basic plane with water-wetted surface, and wherein said aquaporin covers the described bilayer area of at least 1%,
C) optional repetition step b) to obtain the bilayer of multiple fusion,
The permeable carrier d) by second with the basic plane of water-wetted surface deposits to step b) or c) in obtain described lipid bilayer on, to obtain sandwich, and
E) optionally the sandwich of gained is encapsulated in permeability stabilized membrane.
25. 1 kinds of methods preparing moisture film, it comprises the following steps:
A) lipid microcapsule obtained containing aquaporin aquaporin is steeped, and described aquaporin aquaporin accounts at least 0.1%mol/mol of described microcapsule bubble,
B) by described Vesicle fusion in planar lipid bilayer, described planar lipid bilayer is assembled in around the permeable carrier of the basic plane with hydrophobic surface, and wherein said aquaporin covers the described bilayer area of at least 1%, and
C) optionally the sandwich of gained is enclosed in permeability stabilized membrane.
26. 1 kinds of methods preparing ultra-pure water filtrate, it comprises by the water film filtering aqueous solution any one of item 1 ~ 23, to retain ion, particle, organic substance and colloid, described filtrate is substantially not containing the water of ion, particle, organic substance and colloid thus.
27. 1 kinds for producing the reverse osmosis water filter of desalted water from saline source, described desalted water can be used for Irrigation farming and/or is used as drinking water, and wherein at least one final reverse osmosis filter membrane replaces with the moisture film comprising functional aquaporin aquaporin.
28. 1 kinds for producing the reverse osmosis water filter of ultra-pure water from thick water source, described ultra-pure water can be used in semi-conductor industry and/or pharmaceuticals industry, and wherein at least one final reverse osmosis filter membrane replaces with the moisture film comprising functional aquaporin aquaporin.
29. 1 kinds for producing the reverse osmosis water filter of pure water from thick water source, it is for municipal water industry, chemical 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, and wherein at least one final reverse osmosis filter membrane replaces with the moisture film comprising functional aquaporin aquaporin.
30. water filtering devices any one of item 27 ~ 29, wherein apply osmotic pressure to the downstream of described moisture film.
31. according to the water filtering device of item 30, and wherein said osmotic pressure is greater than the concentrated solution at water source to be purified from osmotic pressure.
32. water filtering devices any one of item 27 ~ 31, the wherein said moisture film comprising functional aquaporin aquaporin is the moisture film any one of item 1 ~ 22.
33. 1 kinds of water filtering devices for extraction and recycle-water from body fluid such as urine, milk and sweat, it comprises the moisture film containing functional aquaporin aquaporin, such as, moisture film any one of item 1 ~ 22.
The method of 34. 1 kinds of water obtained from water source for purifying, described method comprises filters by the water filtering device any one of item 27 ~ 33 water obtained from described water source.
35. 1 kinds of hydrophobic polymer films comprising multiple perforation, wherein said perforation be uniformly distributed in the film and in midplane between 2 surfaces of described film substantially all described perforation all there is substantially identical geometry.
36. according to the film of item 35, wherein each described perforation all have even as big as allow steam by but be small enough to the aperture area that prevents aqueous water from passing through, such as 100nm 2~ 1mm 2the area of scope.
37. according to the film of item 35, and wherein said perforation has the greatest cross-section length of millimeter ~ micrometer range.
38. films any one of item 35 ~ 37, wherein said film has the thickness of millimeter ~ micrometer range.
39. films any one of item 35 ~ 38, the geometry of wherein said perforation is selected from circle and ellipse.
40. films any one of item 35 ~ 39, wherein said perforation has substantially identical size.
41. films any one of item 35 ~ 40, wherein said film is selected from the hydrophobic film had as limited in item 13, such as parafilm or poly tetrafluoroethylene.
42. 1 kinds of films, it comprises the sandwich with at least two perme-able support layers, and described at least two perme-able support layers are separated by least one lipid bilayer comprising functional transmembrane proteins.
43. according to the film of item 42, and it comprises the feature limited any one of item 2 ~ 9.
44. 1 kinds of films, it comprises the sandwich with at least two lipid monolayer, when it is combined into a bilayer, described sandwich comprises functional transmembrane proteins, and described at least two lipid monolayer are separated by least one perme-able support layers.
45. according to the film of item 44, and it comprises the feature any one of item 12 ~ 17.

Claims (20)

1. for the reverse osmosis water filter from thick water source or saline source production purified water, wherein said device comprises film, functional aquaporin passage or water-glycerol channel protein channel are recombinated and convert supporting course in lipid vesicle in the film, to form water filtration film, the hydrone existed in described thick water source or saline source can produce purified water through described water filtration film.
2. reverse osmosis water filter according to claim 1, wherein said aquaporin passage is plant origin.
3. reverse osmosis water filter according to claim 2, the aquaporin passage of wherein said plant origin is selected from TIP, PIP or NIP aquaporin and composition thereof and heterozygote.
4. reverse osmosis water filter according to claim 1, wherein said film comprises water-glycerol channel protein channel.
5. reverse osmosis water filter according to claim 1, wherein said aquaporin passage is selected from GLPA passage, GLPB1 passage, GLPB2 passage, GLPB3 passage and GLPY2 passage and composition thereof and heterozygote.
6. the reverse osmosis water filter any one of aforementioned claim, wherein said aquaporin passage or described water-glycerol channel protein channel are mutant proteins.
7. reverse osmosis water filter as claimed in one of claims 1-6, wherein said supporting course has hydrophilic film surface.
8. reverse osmosis water filter according to claim 7, wherein said supporting course comprises the material being selected from mica or polymer.
9. reverse osmosis water filter according to claim 8, wherein said mica is mica tape.
10. reverse osmosis water filter according to claim 8, wherein said polymer is polysulfones or cellulose.
11. reverse osmosis water filters as claimed in one of claims 1-10, wherein said membrane closure is in the porous or osmotic membranes of stabilisation.
12. reverse osmosis water filters any one of claim 1-11, wherein said device comprises multiple film to provide multi-layer filtrating equipment.
13. reverse osmosis water filters any one of claim 1 to 12 are used for the purposes extracting water from hydrous matter or solution.
14. purposes according to claim 13, wherein obtain the solute of the increase concentration be dissolved in described hydrous matter or solution.
15. 1 kinds of methods preparing ultra-pure water filtrate, it comprises by the reverse osmosis water filtration devices aqueous solution any one of claim 1 to 12, to retain ion, particle, organic substance and colloid, described filtrate is substantially not containing the water of ion, particle, organic substance and colloid thus.
16. methods according to claim 15, wherein apply osmotic pressure to the downstream of described moisture film.
17. methods according to claim 16, wherein said osmotic pressure is greater than the concentrated solution at water source to be purified from osmotic pressure.
18. methods according to claim 17, wherein add the nontoxic of high concentration and the solute of easily removing in new Water Room, to promote the normal osmotic pressure of cross-film.
19. methods any one of claim 15-18, wherein said method is used for extracting and recycle-water from body fluid.
20. methods according to claim 19, wherein said body fluid is selected from urine, milk and sweat.
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