CN113332862A - Dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane and preparation method thereof - Google Patents
Dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane and preparation method thereof Download PDFInfo
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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
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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Abstract
The invention discloses a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane and a preparation method thereof. The dialysis/adsorption difunctional nanofiber composite-based hemodialysis membrane sequentially comprises a polyvinyl alcohol hydrogel skin layer and a membrane containing UiO-66- (COOH) from top to bottom2The nanofiber of nanoparticles adsorbs the support layer. In the invention, UiO-66- (COOH)2Nanoparticles immobilized on a nanoparticle with high porosity and interconnected macroporesAnd (3) coating a gel separation layer on the rice fiber membrane serving as an adsorption support layer of the composite membrane to prepare the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane. The adsorption supporting layer realizes the regeneration of the dialysate by exerting the adsorption effect on the toxin, reduces the dosage of the dialysate and realizes the light hemodialysis. The difunctional nanofiber composite-based hemodialysis membrane disclosed by the invention has important significance for development of wearable artificial kidney.
Description
Technical Field
The invention relates to a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane and a preparation method thereof, belonging to the technical field of biological materials.
Background
Kidney disease has become one of the high morbidity, high mortality diseases in humans, with about 6 million people worldwide suffering from kidney disease and is also growing at a rapid pace. In our country, chronic kidney disease patients approach 1.2 million people, with up to 200 million patients developing end stage renal disease. How to effectively treat kidney diseases such as renal failure and the like has become a research hotspot of world researchers. In recent years, hemodialysis technology has become one of the effective therapeutic means for treating patients with end-stage renal disease. Conventional hemodialysis requires periodic treatment of a patient to a stationary dialysis center, which is an intermittent treatment process that consumes large amounts of dialysate. In order to allow patients to receive stable treatment for a long period of time, it is important that hemodialysis be miniaturized for convenience of home or wearing. The problem that needs to be solved at first is how to reduce the volume of dialysate and realize lightweight hemodialysis. In this regard, the concept of wearable artificial kidneys was proposed and developed. Wearable artificial kidney has introduced dialysate regeneration system in the dialysate, mainly is through the adsorption of adsorbent with toxin absorption for the dialysate can cyclic utilization, realizes lightweight hemodialysis so that family or dress use with the volume that reduces the dialysate.
The metal organic framework Materials (MOFs) are a novel porous nano material, have high specific surface area and a large number of functional groups, and are ideal materials for adsorption. Wherein, UiO-66- (COOH)2As a zirconium-based MOF material, the material is easy to prepare, has a stable structure, has a large number of oxygen-containing functional groups which can serve as adsorption sites, and has an excellent adsorption effect on uremic toxins. However, UiO-66- (COOH)2The nano particles are difficult to separate from the liquid matrix in the adsorption process, are not easy to recover and are easy to manufactureCausing secondary pollution, therefore, UiO-66- (COOH)2It is important that the nanoparticles are combined with other easily recyclable substrate materials.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the material used for adsorbing toxin in hemodialysis is difficult to separate from a liquid matrix in the adsorption process, is not easy to recover, is easy to cause secondary pollution, and solves the problems of how to realize light hemodialysis and the like.
In order to solve the technical problem, the invention provides a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane which sequentially comprises a hydrogel skin layer and a membrane containing UiO-66- (COOH) from top to bottom2The nanofiber of nanoparticles adsorbs the support layer.
Preferably, the hydrogel skin layer is a polyvinyl alcohol hydrogel skin layer, and the thickness of the hydrogel skin layer is 0.5-0.6 μm; the thickness of the nanofiber adsorption supporting layer is 80-200 mu m, and the porosity is 70-80%.
The invention also provides a preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane, which comprises the following steps:
step 1: pyromellitic acid and zirconium tetrachloride are dissolved in a solvent, and then UiO-66- (COOH) is synthesized by a hydrothermal method2A nanoparticle;
step 2: mixing UiO-66- (COOH)2Dispersing the nanometer particles in a solvent, adding a polymer material to prepare a spinnable electrostatic spinning solution, and then performing electrostatic spinning to obtain the solution containing UiO-66- (COOH)2A nanofiber membrane of nanoparticles;
and step 3: carrying out cold pressing treatment on the nanofiber membrane obtained in the step 2 to obtain a nanofiber adsorption supporting layer;
and 4, step 4: and (3) dissolving polyvinyl alcohol in water, adjusting the pH value to be acidic, adding glutaraldehyde for crosslinking to obtain polyvinyl alcohol coating liquid, coating the polyvinyl alcohol coating liquid on the nanofiber adsorption supporting layer obtained in the step (3), sealing at room temperature, and after crosslinking is completed, obtaining the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane.
Preferably, the mass ratio of pyromellitic acid to zirconium tetrachloride in the step 1 is 0.5-2: 1; the solvent is a mixed solution of water and acetic acid, wherein the volume ratio of the water to the acetic acid is 3: 2; the reaction temperature of the hydrothermal method is 90-120 ℃, and the reaction time is 24-36 h.
Preferably, the solvent in step 2 includes at least one of N, N-dimethylformamide, N-dimethylacetamide, water, ethanol, isopropanol, N-butanol, acetone, 1, 4-dioxane, dichloromethane, chloroform, tetrahydrofuran, and acetic acid.
Preferably, the polymer material in step 2 comprises at least one of polyacrylonitrile PAN, polyethersulfone PES, polyvinylidene fluoride PVDF, polysulfone PSU, polystyrene PS, polyvinyl chloride PVC, cellulose acetate CA, polycaprolactone PCL, polylactic acid PLA, polyvinyl alcohol PVA, sodium alginate SA, gelatin GE, and modified polymers of the foregoing materials.
Preferably, in the spinnable electrostatic spinning solution in the step 2, the concentration of the polymer material is 5-20 wt%, UiO-66- (COOH)2The mass ratio of the nanoparticles to the polymer material is 0.25-2: 1.
Preferably, the electrostatic spinning in step 2 has the following process parameters: the electrospinning voltage is 20-50 kV, the pore diameter of a spinneret orifice is 0.1-5 mm, the spinning advancing speed is 2-250 mu L/min, the temperature of a spinning environment is 25-55 ℃, the relative humidity of the spinning environment is 20-50%, the receiving distance is 15-35 cm, and the rotating speed of a receiving rotary drum is 400-1000 r/min.
Preferably, the pressure of the cold pressing treatment in the step 3 is 2-10 MPa, and the time is 20-300 s.
Preferably, the concentration of the polyvinyl alcohol in the polyvinyl alcohol coating liquid in the step 4 is 0.1-5 wt%, and the concentration of the glutaraldehyde is 40-50 μ L/g; the pH value is 1-2; the crosslinking time is 15-22min, and the temperature is 20-30 ℃.
The technical principle of the invention is as follows: the invention takes the nano-fiber membrane with high porosity and through macroporous structure as the supporting layer of the composite membrane, and the UiO-66- (COOH) with toxin adsorption effect2Into which the nano-particles are introduced,the hydrogel has the advantages that the hydrogel not only has a supporting function, but also has the function of adsorbing and removing toxins in dialysate, the surface layer of the hydrogel of the polyvinyl alcohol is uniform and compact, the thickness of the hydrogel is controllable, and the toxins in blood can efficiently pass through and block important proteins in blood. Therefore, when the hemodialysis device is applied to hemodialysis, toxins in blood enter dialysate through the surface layer, and the toxins in the dialysate are adsorbed and removed by the substrate, so that the synchronous purification of the blood and the dialysate is realized, and the volume of the dialysate is expected to be reduced, so that the light hemodialysis is realized.
Compared with the prior art, the invention has the beneficial effects that:
1. the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane has a double-layer composite membrane structure, has good permeability, excellent separation performance and good biocompatibility, has a good adsorption effect on toxins by a supporting layer, and can simultaneously remove the toxins in dialysate in a dialysis process, so that the dialysate can be recycled, the volume of the required dialysate is smaller, and light hemodialysis can be realized;
2. the preparation method is simple and easy to implement, and can realize large-scale production.
Drawings
FIG. 1 shows that the compound of example 1 contains UiO-66- (COOH)2Scanning electron microscope images of the nanofiber adsorption support layer of the nanoparticles;
FIG. 2 is an electron microscope scan of the PVA hydrogel skin layer of example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane sequentially comprises a polyvinyl alcohol hydrogel skin layer and a membrane containing UiO-66- (COOH) from top to bottom2The nanofiber of nanoparticles adsorbs the support layer. The thickness of the polyvinyl alcohol hydrogel layer was about 0.6 μm; the nanofiber adsorbent support layer had a thickness of about 100 μm and a porosity of 75%.
The preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane comprises the following steps:
step 1: 5.08g of pyromellitic acid and 4.86g of zirconium tetrachloride were weighed and uniformly dissolved in a mixed solution of water and acetic acid, wherein 120mL of water and 80mL of acetic acid were added. After ultrasonic treatment for 20min, transferring into oil bath pan, and heating and stirring at 100 deg.C for 24 hr to obtain white powdery UiO-66- (COOH)2. Finally, the obtained UiO-66- (COOH)2The powder was washed three times with anhydrous methanol and soaked in acetone in a centrifuge tube for 5 days and centrifuged to replace fresh acetone each day.
Step 2: 1.2g of UiO-66- (COOH) are weighed2The powder was dispersed in 9.2g of N, N-dimethylformamide to obtain a uniform dispersion, 0.8g of polyacrylonitrile powder was added thereto, and stirring was continued at room temperature for 48 hours to completely dissolve it to form a uniform spinning solution. Filling the electrostatic spinning solution into an injector, controlling extrusion by a micro-injection pump, connecting a nozzle of the injector with a high-voltage anode, carrying out electrostatic spinning to obtain the mixture of UiO-66- (COOH) with the spinning voltage of 22kV, the aperture of the nozzle of 0.7mm, the solution advancing speed of 16.7 mu L/min, the ambient temperature of 28 ℃, the relative air humidity of 30 percent, the receiving distance of 20cm and the rotating speed of a receiving roller of 600r/min2A nanofiber membrane of nanoparticles (UNM). The nano-fiber adsorption support layer is used as a nano-fiber adsorption support layer after being subjected to cold pressing treatment for 30s under the pressure of 6 MPa. In addition, as a control, 0.8g of polyacrylonitrile was dissolved in 9.2g of N, N-dimethylformamide to prepare a spinning solution, and the nanofiber support layer was prepared by the same spinning and cold pressing conditions.
And step 3: 2g of polyvinyl alcohol is weighed and dissolved in 98g of deionized water, and the solution is uniformly stirred for 4 hours at the temperature of 60 ℃ to obtain clear and transparent solution. 5g of the solution was taken, pH adjusted to L, 220. mu.L of glutaraldehyde was added, and after crosslinking for 18min at 25 ℃ ambient temperature, the doped UiO-66- (COOH) obtained in step 2 was coated with a 10 μm spatula2Placing the coated membrane on a nanofiber (UNM) adsorption supporting layer of nanoparticles in a watch glass, sealing at room temperature for 12h, taking out, cleaning with deionized water, and soaking in deionized water for storage to obtain the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane, wherein the hemodialysis membrane contains UiO-66- (COOH)2Electron microscope scan images of the nanofiber adsorptive support layer and the polyvinyl alcohol hydrogel skin layer of the nanoparticles are respectively shown in fig. 1 and fig. 2. For reference, the coating solution is coated on the nanofiber supporting layer prepared in the step 2 to obtain the nanofiber composite membrane.
The nanofiber composite membrane and the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane prepared in the above way are subjected to a 4-hour dialysis experiment test respectively (creatinine: 150mg/L, albumin: L g/L, dialysate flow rate: 500mL/min, and simulated blood flow rate: 10 mL/min). When the volume of the dialysate is 2000mL, the creatinine clearance of the nanofiber composite membrane is 63.2%, and the albumin clearance is 1.5%. When the volume of the dialysate is 200mL, the creatinine clearance rate of the nanofiber composite membrane is 49.5%, and the albumin clearance rate is 1.6%; the creatinine clearance rate of the dialysis/adsorption bifunctional nanofiber composite hemodialysis membrane is 63%, and the albumin clearance rate is 1.5%. Therefore, when the same toxin removing effect is achieved, the volume of the dialysis liquid can be reduced to one tenth of the original volume when the dialysis/adsorption nanofiber composite membrane is applied, and the light weight is realized.
Example 2
A dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane sequentially comprises a polyvinyl alcohol hydrogel skin layer and a membrane containing UiO-66- (COOH) from top to bottom2The nanofiber of nanoparticles adsorbs the support layer. The thickness of the polyvinyl alcohol hydrogel layer was about 0.6 μm; the thickness of the nanofiber adsorbent support layer was about 120 μm and the porosity was 80%.
The preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane comprises the following steps:
step 1: 4.06g of pyromellitic acid and 3.89g of zirconium tetrachloride were weighed and uniformly dissolved in a mixed solution of dehydrated water and acetic acid, wherein 96mL of water and 64mL of acetic acid were added. After sonication for 20min, it was transferred to an oil bath and heated at 100 ℃ for 24h to give white powder UiO-66- (COOH)2. Finally, the obtained UiO-66- (COOH)2The powder was washed three times with anhydrous methanol and soaked in acetone in a centrifuge tube for 5 days and centrifuged to replace fresh acetone each day.
Step 2: 0.8g of UiO-66- (COOH) was weighed2The powder was dispersed in 9.2g of N, N-dimethylformamide to form a homogeneous dispersion, 0.8g of polyacrylonitrile powder was added thereto, and stirred at room temperature for 48 hours to completely dissolve it to form a uniform spinning solution. Filling the electrostatic spinning solution into an injector, controlling extrusion by a micro-injection pump, connecting a nozzle of the injector with a high-voltage anode, carrying out electrostatic spinning at a spinning voltage of 22kV, a nozzle aperture of 0.7mm, a solution advancing speed of 16.7 mu L/min, an ambient temperature of 28 ℃, an air relative humidity of 30%, a receiving distance of 20cm and a receiving roller rotation speed of 600r/min to obtain the mixture of UiO-66- (COOH)2A nanofiber membrane of nanoparticles (UNM). The nano-fiber adsorption support layer is used as a nano-fiber adsorption support layer after being subjected to cold pressing treatment for 30s under the pressure of 6 MPa. In addition, as a control, 0.8g of polyacrylonitrile was dissolved in 9.2g of N, N-dimethylformamide to prepare a spinning solution, and the nanofiber support layer was prepared by the same spinning and cold pressing conditions.
And step 3: 2g of polyvinyl alcohol is weighed and dissolved in 98g of deionized water, and the solution is uniformly stirred for 4 hours at the temperature of 60 ℃ to obtain clear and transparent solution. And (3) taking 5g of solution, adjusting pH to L, adding 220 mu L of glutaraldehyde, crosslinking for 18min at the ambient temperature of 25 ℃, coating a scraper with the thickness of 10 mu m on the nanofiber adsorption supporting layer prepared in the step (2), putting the coated membrane into a surface dish, sealing for 12h at room temperature, taking out, washing with ionized water, and soaking and storing in deionized water to obtain the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane. For reference, the coating solution is coated on the nanofiber supporting layer prepared in the step 2 to obtain the nanofiber composite membrane.
The prepared nanofiber composite membrane and the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane are subjected to 4-hour dialysis experimental tests respectively (creatinine: 150mg/L, albumin: L g/L, dialysate flow rate: 500mL/min, and simulated blood flow rate: 10 mL/min). When the volume of the dialysate is 2000mL, the creatinine clearance of the nanofiber composite membrane is 63.2%, and the albumin clearance is 1.4%. When the volume of the dialysate is 200mL, the creatinine clearance rate of the nanofiber composite membrane is 50%, and the albumin clearance rate is 1.5%; the creatinine clearance rate of the dialysis/adsorption bifunctional nanofiber composite hemodialysis membrane is 63.5%, and the albumin clearance rate is 1.5%. Therefore, when the same toxin removing effect is achieved, the volume of the dialysis liquid can be reduced to one tenth of the original volume when the dialysis/adsorption nanofiber composite membrane is applied, and the light weight is realized.
Example 3
A dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane sequentially comprises a polyvinyl alcohol hydrogel skin layer and a membrane containing UiO-66- (COOH) from top to bottom2The nanofiber of nanoparticles adsorbs the support layer. The thickness of the polyvinyl alcohol hydrogel layer was about 0.6 μm; the nanofiber adsorbent support layer had a thickness of about 150 μm and a porosity of 80%.
The preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane comprises the following steps:
step 1: 4.06g of pyromellitic acid and 3.89g of zirconium tetrachloride were weighed and uniformly dissolved in a mixed solution of water and acetic acid, wherein 96mL of water and 64mL of acetic acid were used. After sonication for 20min, it was transferred to an oil bath and heated at 100 ℃ for 24 hours to give white powder UiO-66- (COOH)2. Finally, the obtained UiO-66- (COOH)2The powder was washed three times with anhydrous methanol and soaked in acetone in a centrifuge tube for 5 days and centrifuged to replace fresh acetone each day.
Step 2: 0.4g of UiO-66- (COOH) was weighed2The powder was dispersed in 9.2g of N, N-dimethylformamide to form a homogeneous dispersion, 0.8g of polyacrylonitrile powder was added thereto, and stirred at room temperature for 48 hours to completely dissolve it to form a uniform spinning solution. Filling the electrostatic spinning solution into an injector, controlling extrusion by a micro-injection pump, connecting a nozzle of the injector with a high-voltage anode, carrying out electrostatic spinning at a spinning voltage of 22kV, a nozzle aperture of 0.7mm, a solution advancing speed of 16.7 mu L/min, an ambient temperature of 28 ℃, an air relative humidity of 30%, a receiving distance of 20cm and a receiving roller rotation speed of 600r/min to obtain the mixture of UiO-66- (COOH)2Nanofiber membranes of nanoparticles. The nano-fiber adsorption support layer is used as a nano-fiber adsorption support layer after being subjected to cold pressing treatment for 30s under the pressure of 6 MPa. In addition, as a control, 0.8g of polyacrylonitrile was dissolved in 9.2g of N, N-dimethylformamide to prepare a spinning solution, which was passed throughAnd preparing the nanofiber supporting layer under the same spinning and cold pressing conditions.
And step 3: 2g of polyvinyl alcohol is weighed and dissolved in 98g of pure water, and the solution is evenly stirred for 4 hours at 60 ℃ to obtain clear and transparent solution. And (3) taking 5g of solution, adjusting pH to L, adding 220 mu L of glutaraldehyde, crosslinking for 18min at the ambient temperature of 25 ℃, coating a scraper with the thickness of 10 mu m on the nanofiber adsorption supporting layer prepared in the step (2), putting the coated membrane into a surface dish, sealing for 12h at room temperature, taking out, washing with ionized water, and soaking and storing in deionized water to obtain the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane. Similarly, as a control, the coating solution was applied to the nanofiber support layer prepared in step 2 to obtain a nanofiber composite membrane.
The prepared nanofiber composite membrane and the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane are subjected to 4-hour dialysis experimental tests respectively (creatinine: 150mg/L, albumin: L g/L, dialysate flow rate: 500mL/min, and simulated blood flow rate: 10 mL/min). When the volume of the dialysate is 2000mL, the creatinine clearance of the nanofiber composite membrane is 63.2%, and the albumin clearance is 1.4%. When the volume of the dialysate is 200mL, the creatinine clearance rate of the nanofiber composite membrane is 50%, the albumin clearance rate is 1.5%, the creatinine clearance rate of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane is 63.5%, and the albumin clearance rate is 1.5%. Therefore, when the same toxin removing effect is achieved, the dialysis liquid volume can be reduced to one tenth of the original volume when the dialysis/adsorption bifunctional nanofiber composite hemodialysis membrane is applied, and the light weight of the hemodialysis membrane is realized.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.
Claims (10)
1. A dialysis/adsorption difunctional nanofiber composite-based hemodialysis membrane is characterized in that the hemodialysis membrane is prepared from the topComprises hydrogel skin layer and the hydrogel skin layer comprises UiO-66- (COOH)2The nanofiber of nanoparticles adsorbs the support layer.
2. The dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane of claim 1, wherein the hydrogel skin layer is a polyvinyl alcohol hydrogel skin layer, and the thickness of the hydrogel skin layer is 0.5-0.6 μm; the thickness of the nanofiber adsorption supporting layer is 80-200 mu m, and the porosity is 70-80%.
3. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane of claim 1 or 2, comprising the steps of:
step 1: pyromellitic acid and zirconium tetrachloride are dissolved in a solvent, and then UiO-66- (COOH) is synthesized by a hydrothermal method2A nanoparticle;
step 2: mixing UiO-66- (COOH)2Dispersing the nanometer particles in a solvent, adding a polymer material to prepare a spinnable electrostatic spinning solution, and then performing electrostatic spinning to obtain the solution containing UiO-66- (COOH)2A nanofiber membrane of nanoparticles;
and step 3: carrying out cold pressing treatment on the nanofiber membrane obtained in the step 2 to obtain a nanofiber adsorption supporting layer;
and 4, step 4: and (3) dissolving polyvinyl alcohol in water, adjusting the pH value to be acidic, adding glutaraldehyde for crosslinking to obtain polyvinyl alcohol coating liquid, coating the polyvinyl alcohol coating liquid on the nanofiber adsorption supporting layer obtained in the step (3), sealing at room temperature, and after crosslinking is completed, obtaining the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane.
4. The preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the mass ratio of pyromellitic acid to zirconium tetrachloride in the step 1 is 0.5-2: 1; the solvent is a mixed solution of water and acetic acid, wherein the volume ratio of the water to the acetic acid is 3: 2; the reaction temperature of the hydrothermal method is 90-120 ℃, and the reaction time is 24-36 h.
5. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the solvent in the step 2 comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, water, ethanol, isopropanol, N-butanol, acetone, 1, 4-dioxane, dichloromethane, chloroform, tetrahydrofuran, and acetic acid.
6. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the polymer material in the step 2 comprises at least one of polyacrylonitrile PAN, polyethersulfone PES, polyvinylidene fluoride PVDF, polysulfone PSU, polystyrene PS, polyvinyl chloride PVC, cellulose acetate CA, polycaprolactone PCL, polylactic acid PLA, polyvinyl alcohol PVA, sodium alginate SA, gelatin GE, and modified polymers of the foregoing materials.
7. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the concentration of the polymer material in the spinnable electrospinning solution in the step 2 is 5-20 wt%, UiO-66- (COOH)2The mass ratio of the nanoparticles to the polymer material is 0.25-2: 1.
8. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the electrostatic spinning in the step 2 has the following process parameters: the electrospinning voltage is 20-50 kV, the pore diameter of a spinneret orifice is 0.1-5 mm, the spinning advancing speed is 2-250 mu L/min, the temperature of a spinning environment is 25-55 ℃, the relative humidity of the spinning environment is 20-50%, the receiving distance is 15-35 cm, and the rotating speed of a receiving rotary drum is 400-1000 r/min.
9. The preparation method of the dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the pressure of the cold pressing treatment in the step 3 is 2-10 MPa, and the time is 20-300 s.
10. The method for preparing a dialysis/adsorption bifunctional nanofiber composite-based hemodialysis membrane according to claim 3, wherein the polyvinyl alcohol coating solution in the step 4 has a polyvinyl alcohol concentration of 0.1 to 5 wt%, and a glutaraldehyde concentration of 40 to 50 μ L/g; the pH value is 1-2; the crosslinking time is 15-22min, and the temperature is 20-30 ℃.
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