CN109647225A - A kind of compound hemodialysis membrane of nanofiber and its preparation removing channel containing orientation toxin - Google Patents
A kind of compound hemodialysis membrane of nanofiber and its preparation removing channel containing orientation toxin Download PDFInfo
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- CN109647225A CN109647225A CN201910058887.2A CN201910058887A CN109647225A CN 109647225 A CN109647225 A CN 109647225A CN 201910058887 A CN201910058887 A CN 201910058887A CN 109647225 A CN109647225 A CN 109647225A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
It is the polyvinyl alcohol separating layer containing heparin functionalized carbon nano-tube the present invention relates to a kind of compound hemodialysis membrane of nanofiber containing orientation toxin removal channel and its preparation, the cortex of the dialysis membrane, supporting layer is polyacrylonitrile nanofiber film.In the present invention the heparin functionalized carbon nano-tube in cortex and between polyvinyl alcohol matrix interface formed nano gap provide the nanochannel of orientation for toxin, compound hemodialysis membrane is not under the premise of sacrificing macro-molecular protein selectivity made from this method, with efficient small, middle molecule toxins removal rate, while also showing excellent blood compatibility.
Description
Technical field
The invention belongs to composite material dialysis membrane and its preparation fields, in particular to a kind of to remove channel containing orientation toxin
The compound hemodialysis membrane of nanofiber and its preparation.
Background technique
The whole world has millions of people with kidney trouble according to statistics, and kidney failure, which has become, endangers one of disease of human health.
Acute and chronic renal failure will lead to the intracorporal toxin of people and increase, and then cause body adverse reaction even uremia.Blood is saturating
Analysis is considered as most viable effective clinical alternative medicine, and has been used more than 50 years as long as.In dialyzer, dialysis membrane will
Blood and dialyzate separate, and small, the middle molecule toxins in blood are removed by the diffusion of dialysis membrane and convection action, while people
Macromolecular plasma protein necessary to body is then retained by the sieving actoion of dialysis membrane aperture.However, due to the inherency of dialysis membrane
Matter, it is still unsatisfactory to the removal rate of toxin by the dialysis membrane of prior art preparation, lead to the patient of certain dialysis ages
The death rate is still higher.Therefore, it is to improve patient's prognosis that exploitation, which has the more efficient high-performance hemodialysis membrane for removing toxin,
It is crucial.
With the development of modern science, a variety of materials and technology have been used for the exploitation of dialysis membrane.Cellulose and its derivates
It is first generation Hemodialysis Membrane Material, the dialysis membrane structure of this kind of material preparation is uniformly and fine and close, therefore it can only allow molecular weight
Toxin less than 2000Da slow transits through.In order to remove the toxin of higher molecular weight, the material of cellulose base in the past few years
Replaced artificial-synthetic copolymer's material, common are polysulfones, polyether sulfone, polyacrylonitrile, Kynoar, polylactic acid and
Polyvinyl alcohol etc..This kind of dialysis membrane has asymmetric structure, and removable molecular weight is up to the toxin of 5000Da, but to molecular weight
It still cannot be removed effectively in the middle molecule toxins of 5000Da or more.In order to remove this kind of middle molecule toxins, the prior art mainly collects
In in the exploitation of optimization or new additive to dialysis membrane preparation process.For example, being 105148748 B's of CN in notification number
In Chinese invention patent, the microcellular structure of polylactic acid hemodialysis membrane is regulated and controled by situ aggregation method.It is CN in notification number
In the Chinese invention patent of 105833748 B, polyacrylonitrile matrix is added to using polyglycolic acid and chitosan as additive
In prepare high flux hemodialysis film.In the Chinese invention patent that notification number is 105311974 B of CN, turned by atom
It moves radical polymerization and prepares the triblock copolymer containing polysulfones and acrylic acid, then it is blended with polysulfones to improve blood
The performance of dialysis membrane.However, it is all these by non-solvent induction phase separation method (i.e. polymer dissolve in a solvent after non-
The method of precipitating film forming is precipitated in solvent) dialysis membrane of preparation because it is with wider pore-size distribution, therefore will usually face infiltration
Tradeoff between permeability (i.e. toxin how soon pass through film) and selectivity (i.e. the reserving degree of high molecular weight protein).Pass through existing skill
Art can increase the average pore size of dialysis membrane, it is made to improve the removal rate to middle molecule toxins to a certain extent, but sacrificial simultaneously
Selectivity of the domestic animal to high molecular weight protein.It is 105727771 B of CN in notification number to break this universal upper limit relationship
Chinese invention patent in, be prepared for the modified compound hemodialysis membrane of polyvinyl alcohol hydrogel thin layer nanofiber of heparan,
Toxin removal rate can be improved with the nanofiber supporting layer for interconnecting open-celled structure.But for polymer film, porosity
Usually be limited, and hole is limited in a manner of tortuous by polymer chain, thus to the removal ability of toxin still by
To very big limitation.To make composite membrane reach the maximum removal ability to toxin, polyvinyl alcohol cortex leads to the modified increase of heparan
The average pore size of film, but it only maintains 90% or so to the rejection of macro-molecular protein.So in holding dialysis membrane to big
Improving while molecule protein is highly selective is a huge challenge to the removal ability of toxin.
In recent years, the concept of nanochannel causes the extensive concern of people.Because it is provided for Auto-regulator transport
A kind of new strategy,.The development of nano material is also applied to every field, including filtering, the energy and biomedicine etc..It grinds
The interface zone studied carefully between discovery carbon nanotube and polymer substrate can provide efficient nanochannel for molecule transport, therefore
Huge potentiality are shown in polymer film systems.However, the not phase between inorganic carbon nanotube and organic polymer matrix
Capacitive and the potential toxicity of carbon nanotube become applied two need solved in haemodialysis field it is main
Problem.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of nanofiber containing orientation toxin removal channel is compound
Hemodialysis membrane and its preparation overcome prior art material is poor to the removal rate of toxin, inorganic carbon nanotube and organic polymer
The defect of the potential toxicity of incompatibility and carbon nanotube between object matrix etc., this method are prepared for heparin functionalization first
Carbon nanotube, be then introduced in the separating layer of nano-fiber composite film, the carbon nanotube of heparin functionalization with polymerize
Between object matrix there is the nano gap between good compatibility and two-phase to provide the nanochannel of orientation for the transport of toxin,
The compound dialysis membrane of obtained nanofiber has high toxin removal rate, high protein rejection and excellent blood compatibility.
The compound hemodialysis membrane of a kind of nanofiber of the invention, the cortex of the dialysis membrane are to contain heparin functionalized carbon
The polyvinyl alcohol separating layer of nanotube, supporting layer are polyacrylonitrile nanofiber film.
Effective average pore size of the superficial cortical layers is 3-7nm.
In the heparin functionalized carbon nano-tube in cortex and the nano gap of interface formation is between polyvinyl alcohol matrix
Toxin provides the nanochannel of orientation.
The width of the nano gap formed in the cortex is 4-6nm.
A kind of preparation method of compound hemodialysis membrane of nanofiber of the invention, comprising:
(1) dopamine solution, carbon nanotube are mixed, pH value is adjusted after ultrasonic disperse to 8.0~11.0, is stirred at room temperature anti-
6-24h is answered, washed after filtering, be dried to obtain the carbon nanotube that poly-dopamine is sticked；
(2) carbon nanotube that above-mentioned poly-dopamine is sticked is dispersed in water, heparin sodium is added, reaction is stirred at room temperature
24-48h washs after filtering, is dry, obtaining the carbon nanotube of heparin functionalization；
(3) carbon nanotube of above-mentioned heparin functionalization is added in poly-vinyl alcohol solution after ultrasound is evenly dispersed and adjusts pH value
To 1.0~2.0, crosslinking agent is added, is obtained after carrying out precrosslink reaction coated in polyacrylonitrile nanofiber film support layer surface
Compound hemodialysis membrane.
The mass ratio of carbon nanotube and dopamine is 1:1~5:1 in the step (1).
The concentration of dopamine solution is 0.5~5.0mg/mL in the step (1)；The solvent of dopamine solution is that concentration is
The trishydroxymethylaminomethane buffer solution of 5~15mmol/L.
The mass ratio for the carbon nanotube that heparin sodium and poly-dopamine are sticked in the step (2) is 1:1~5:1.
The carbon nanotube that poly-dopamine is sticked in the step (2) is with the concentration ultrasonic disperse of 0.5~5.0mg/mL super
In pure water.
The weight average molecular weight 100 of polyvinyl alcohol in the step (3), 000~200,000, alcoholysis degree 88%；Polyvinyl alcohol
Solution is the solution that polyvinyl alcohol is dissolved in that 5~10h preparation mass fraction is 2% in ultrapure water at a temperature of 50~80 DEG C.
Crosslinking agent is glutaraldehyde in the step (3)；In aldehyde radical and polyvinyl alcohol repetitive unit than adding for 0.25 ratio
Enter glutaraldehyde.
The carbon nanotube of heparin functionalization and mass ratio 1:100~15:100 of polyvinyl alcohol in the step (3).
Polyacrylonitrile nanofiber film is that electrostatic spinning obtains polyacrylonitrile nanofiber film in the step (3), specifically
Are as follows: the polyacrylonitrile that weight average molecular weight is 100,000~150,000 is dissolved in N, N- dimethyl formyl at a temperature of 50~80 DEG C
5~10h prepares the solution that mass fraction is 6~10% in amine, passes through electrostatic spinning.
The electrostatic spinning process parameter are as follows: ambient humidity 30~50%, 25~60 DEG C of environment temperature, voltage 18~
30kV, 15~20 μ L/min of spinning rate, it is 10~25cm that nanofiber, which receives distance,.
The precrosslink time is 25~45min in the step (3).
Polyacrylonitrile nanofiber film supporting layer is in the step (3) with a thickness of 50~100 μm.
The present invention provides a kind of application of compound hemodialysis membrane of the nanofiber, such as effectively removing medium biology
The nano-fiber composite film of molecule.
Beneficial effect
(1) heparin functionalized carbon nano-tube and polyethylene in the compound hemodialysis membrane cortex of nanofiber produced by the present invention
The nano gap that interface is formed between alcohol matrix provides the nanochannel of orientation, compound blood made from this method for toxin
Dialysis membrane has efficient small, middle molecule toxins removal rate under the premise of not sacrificing macro-molecular protein selectivity.Compared to public affairs
Accuse number average hole for increasing film by heparan modified polyvinylalcohol cortex for being 105727771 B Chinese invention patent of CN
The method of diameter, the present invention have constructed additional toxin removal under the premise of having no significant effect the aperture of polyvinyl alcohol cortex
Channel has reached the beneficial effect effectively removed while not sacrificing the rejection of macro-molecular protein to toxin.
(2) the compound hemodialysis membrane of nanofiber produced by the present invention shows excellent blood based on the bioactivity of heparin
Liquid phase capacitive: highly resistance protein adsorption inhibits platelet adhesion reaction, excellent anticoagulant active and lower hemolysis rate.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of the heparin carbon nano tube prepared in embodiment 1.
Fig. 2 is the profile scanning electron microscope of the compound hemodialysis membrane of nanofiber prepared in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
In the compound hemodialysis membrane cortex of nanofiber obtained heparin functionalized carbon nano-tube and polyvinyl alcohol matrix it
Between interface formed nano gap provide the nanochannel of orientation for toxin.
Embodiment 1
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction is stirred at room temperature for 24 hours in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 2:100 by heparin with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol single
Member is coated in polyacrylonitrile nanofiber film supporting layer after 26min precrosslink reaction than glutaraldehyde is added for 0.25 ratio
Surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 5nm, under 0.1Mpa pressure
Pure water flux is 320L/m2H, simulation dialysis 4h is 85% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 50%, while being 98.6% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 28 μ g/cm2, platelet adhesion reaction amount is 5.8x105cell/cm2, blood plasma cover the calcification time be 330s, hemolysis rate 1.7%.
Embodiment 2
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction is stirred at room temperature for 24 hours in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 5:100 by heparin with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol single
Member is coated in polyacrylonitrile nanofiber film supporting layer after 26min precrosslink reaction than glutaraldehyde is added for 0.25 ratio
Surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 6nm, under 0.1Mpa pressure
Pure water flux is 350L/m2H, simulation dialysis 4h is 88% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 55%, while being 98.4% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 24 μ g/cm2, platelet adhesion reaction amount is 3.8x105cell/cm2, blood plasma cover the calcification time be 410s, hemolysis rate 1.5%.
Embodiment 3
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction is stirred at room temperature for 24 hours in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 10:100 by liver with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of plain functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol
Unit is coated in polyacrylonitrile nanofiber film after 26min precrosslink reaction and supports than glutaraldehyde is added for 0.25 ratio
Layer surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 7nm, under 0.1Mpa pressure
Pure water flux is 400L/m2H, simulation dialysis 4h is 92% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 62%, while being 98.2% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 17 μ g/cm2, platelet adhesion reaction amount is 2.3x105cell/cm2, blood plasma cover the calcification time be 490s, hemolysis rate 1.1%.
Embodiment 4
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction 48h is stirred at room temperature in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 2:100 by heparin with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol single
Member is coated in polyacrylonitrile nanofiber film supporting layer after 26min precrosslink reaction than glutaraldehyde is added for 0.25 ratio
Surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 3nm, under 0.1Mpa pressure
Pure water flux is 300L/m2H, simulation dialysis 4h is 83% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 48%, while being 99.2% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 26 μ g/cm2, platelet adhesion reaction amount is 5.1x105cell/cm2, blood plasma cover the calcification time be 340s, hemolysis rate 1.2%.
Embodiment 5
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction 48h is stirred at room temperature in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 5:100 by heparin with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol single
Member is coated in polyacrylonitrile nanofiber film supporting layer after 26min precrosslink reaction than glutaraldehyde is added for 0.25 ratio
Surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 4nm, under 0.1Mpa pressure
Pure water flux is 330L/m2H, simulation dialysis 4h is 85% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 52%, while being 98.8% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 21 μ g/cm2, platelet adhesion reaction amount is 2.1x105cell/cm2, blood plasma cover the calcification time be 440s, hemolysis rate 0.9%.
Embodiment 6
(1) 250mg dopamine is dissolved in 500mL trishydroxymethylaminomethane buffer solution (10mmol/L), is added
500mg carbon nanotube adjusts solution ph to 8.5 after ultrasonic disperse, reaction 12h is stirred at room temperature, uses after filtering
0.02mol/L hydrochloric acid and ultrapure water are dried to obtain the carbon nanotube that poly-dopamine is sticked after washing respectively.
(2) carbon nanotube for sticking poly-dopamine is added with the concentration ultrasonic disperse of 1.0mg/mL in ultrapure water
Reaction 48h is stirred at room temperature in 500mg heparin sodium, with the carbon nanometer for being dried to obtain heparin functionalization after milli-Q water after filtering
Pipe.
(3) polyacrylonitrile that weight average molecular weight is 120,000 is dissolved in N,N-dimethylformamide at 50 °C
8h prepares the solution that mass fraction is 8%, in ambient humidity 45%, 30 DEG C of environment temperature, voltage 24kV, and 16 μ L/ of spinning rate
Min, it is electrostatic spinning under conditions of 20cm that nanofiber, which receives distance, selects the polyacrylonitrile nanofiber with a thickness of 100 μm
Supporting layer of the film as compound hemodialysis membrane.
(4) by weight average molecular weight 146,000, the polyvinyl alcohol of alcoholysis degree 88% is dissolved in 6h in ultrapure water at a temperature of 60 DEG C
The solution that mass fraction is 2% is prepared, is 10:100 by liver with the mass ratio of the carbon nanotube of heparin functionalization and polyvinyl alcohol
The carbon nanotube of plain functionalization is added in solution, and pH value is adjusted after ultrasound is evenly dispersed to 1.5, is repeated with aldehyde radical and polyvinyl alcohol
Unit is coated in polyacrylonitrile nanofiber film after 26min precrosslink reaction and supports than glutaraldehyde is added for 0.25 ratio
Layer surface obtains compound hemodialysis membrane.
Effective average pore size of the compound hemodialysis membrane superficial cortical layers of the nanofiber is 5nm, under 0.1Mpa pressure
Pure water flux is 380L/m2H, simulation dialysis 4h is 89% to the removal rate of small molecule urea, micro- to medium biomolecule β 2-
The removal rate of globulin is 59%, while being 98.4% to high molecular weight protein bovine serum albumin rejection, protein Static Adsorption
Amount is 14 μ g/cm2, platelet adhesion reaction amount is 0.9x105cell/cm2, blood plasma cover the calcification time be 520s, hemolysis rate 0.6%.
Comparative example 1
The highest composite membrane of urea clear index is compared with 105727771 B Chinese invention patent of CN.In CN
In 105727771 B Chinese invention patent embodiments 7, composite membrane is to urea clear index 85%, the removal rate of β2-microglobulin
59%, retention rate of proteins is 91% (clearance rate 9%), and superficial cortical layers aperture 10nm, protein adsorbance is 17 μ g/cm2.And this
In inventive embodiments 6, composite membrane is to urea clear index 89%, and the removal rate of β2-microglobulin is 59%, and retention rate of proteins is
98.4%, superficial cortical layers aperture 5nm, protein adsorbance are 14 μ g/cm2。
By contrast as it can be seen that composite membrane prepared by the present invention is on the basis of effectively removing toxin, to macro-molecular protein
It is logical based on additional toxin removal has been constructed in composite membrane cortex with higher rejection and better blood compatibility
Road, the aperture without significantly increasing polyvinyl alcohol cortex.
Comparative example 2
It is compared with the composite membrane in 105727771 B Chinese invention patent of CN and in the present invention with same apertures.
In CN105727771B Chinese invention patent embodiment 2, composite membrane is to urea clear index 80%, the removal of β2-microglobulin
Rate is 61%, and retention rate of proteins is 95% (clearance rate 5%), and superficial cortical layers aperture 7nm, protein adsorbance is 22 μ g/cm2。
And in the embodiment of the present invention 3, composite membrane is 62% to urea clear index 92%, the removal rate of β2-microglobulin, retention rate of proteins
It is 98.2%, superficial cortical layers aperture 7nm, protein adsorbance is 17 μ g/cm2。
By contrast as it can be seen that composite membrane prepared by the present invention is in the identical situation in aperture, have higher toxin removal rate,
Rate and protein retention and better blood compatibility are to be based on having constructed more toxin removals channel in cortex.
Claims (10)
1. a kind of compound hemodialysis membrane of nanofiber, which is characterized in that the cortex of the dialysis membrane is to contain heparin functionalization
The polyvinyl alcohol separating layer of carbon nanotube, supporting layer are polyacrylonitrile nanofiber film, and the heparin functionalized carbon in cortex is received
Interface forms nano gap as nanochannel between mitron and polyvinyl alcohol matrix.
2. dialysis membrane according to claim 1, which is characterized in that the width of the nano gap is 4-6nm；Cortex is averaged
Aperture is 3-7nm.
3. a kind of preparation method of the compound hemodialysis membrane of nanofiber, comprising:
(1) dopamine solution, carbon nanotube are mixed, pH value is adjusted after ultrasonic disperse to 8.0~11.0, reaction 6 is stirred at room temperature
~for 24 hours, it washed after filtering, be dried to obtain the carbon nanotube that poly-dopamine is sticked；
(2) carbon nanotube that above-mentioned poly-dopamine is sticked is dispersed in water, be added heparin sodium be stirred at room temperature reaction 24~
48h washs after filtering, is dry, obtaining the carbon nanotube of heparin functionalization；
(3) carbon nanotube of above-mentioned heparin functionalization is added in poly-vinyl alcohol solution after ultrasound is evenly dispersed adjust pH value to
1.0~2.0, crosslinking agent is added, is answered after carrying out precrosslink reaction coated in polyacrylonitrile nanofiber film support layer surface
Close hemodialysis membrane.
4. preparation method according to claim 3, which is characterized in that the matter of carbon nanotube and dopamine in the step (1)
Amount is than being 1:1~5:1.
5. preparation method according to claim 3, which is characterized in that heparin sodium sticks with poly-dopamine in the step (2)
Carbon nanotube mass ratio be 1:1~5:1.
6. preparation method according to claim 3, which is characterized in that the weight average molecular weight of polyvinyl alcohol in the step (3)
100,000~200,000, alcoholysis degree 88%；Poly-vinyl alcohol solution is that polyvinyl alcohol is dissolved in ultrapure water at a temperature of 50~80 DEG C
In 5~10h prepare mass fraction be 2% solution.
7. preparation method according to claim 3, which is characterized in that crosslinking agent is glutaraldehyde in the step (3)；By aldehyde radical
With polyvinyl alcohol repetitive unit than glutaraldehyde is added for 0.25 ratio；The carbon nanotube of heparin functionalization and the matter of polyvinyl alcohol
Amount is than 1:100~15:100.
8. preparation method according to claim 3, which is characterized in that polyacrylonitrile nanofiber film is in the step (3)
Electrostatic spinning obtains polyacrylonitrile nanofiber film, specifically: the polypropylene for being 100,000~150,000 by weight average molecular weight
Nitrile is dissolved in 5~10h in n,N-Dimethylformamide at a temperature of 50~80 DEG C and prepares the solution that mass fraction is 6~10%, leads to
Cross electrostatic spinning.
9. preparation method according to claim 3, which is characterized in that polyacrylonitrile nanofiber film branch in the step (3)
Layer is supportted with a thickness of 50~100 μm.
10. a kind of application of the compound hemodialysis membrane of nanofiber described in claim 1.
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