CN110813106B - MOFs modified double-layer structure composite electrospun nanofiber membrane, preparation method and application thereof in blood purification - Google Patents
MOFs modified double-layer structure composite electrospun nanofiber membrane, preparation method and application thereof in blood purification Download PDFInfo
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Abstract
The invention relates to a preparation method of a MOFs (metal-organic frameworks) -modified double-layer-structure composite electrospun nanofiber membrane and application of the MOFs-modified double-layer-structure composite electrospun nanofiber membrane in blood purification. The functionalized nano-fiber dialysis membrane is prepared by combining an electrostatic spinning technology and a hydrothermal method, wherein the lower layer is prepared by taking polyacrylonitrile as a matrix, and polydopamine is coated on the surface of the polyacrylonitrile to improve the hydrophilicity of the polydopamine, so that Cu grows on the outermost layer3(BTC)2Crystal particles; the upper layer is a chitosan/sericin composite nanofiber membrane. The MOFs modified double-layer structure composite electrospun nanofiber membrane can effectively remove urea and creatinine and has excellent simulated hemodialysis effect. The preparation process is simple and easy to implement, raw materials are easy to obtain, the cost is low, and the preparation method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of environment nano new functional materials, and particularly relates to an MOFs (metal-organic frameworks) -modified double-layer structure composite electrospun nanofiber membrane, a preparation method thereof and application thereof in blood purification.
Background
With the progressive aging of our society, the incidence of renal failure caused by the high incidence of diseases such as hypertension and hyperglycemia is continuously increasing. According to statistics, the incidence rate of chronic kidney diseases in China is up to 11 percent and is on the trend of rising year by year; different from European and American countries, glomerulonephritis is the main cause of uremia of Chinese people at present, but the number of chronic renal failure dialysis patients caused by diabetes and hypertension is increasing and becomes mainstream.
Hemodialysis (HD) is one of the alternative treatments for the kidney of patients with acute and chronic renal failure. The method comprises the steps of draining blood in a patient body to the outside of the body, introducing the blood and dialysate of the patient into a dialyzer at the same time by utilizing the principle of a semipermeable membrane, removing toxins in the patient body by means of concentration gradient and pressure gradient on two sides of a dialysis membrane through diffusion, convection and adsorption, removing excessive water retention in the body through ultrafiltration, supplementing substances required by the body, and correcting electrolyte and acid-base balance disorder.
Metal-organic frameworks (MOFs) are a class of organic-inorganic hybrid materials with topological structures, and are synthesized from Metal ions or Metal clusters and organic ligands by self-assembly. In recent decades, metal-organic frameworks have been a new class of materials that has developed quite rapidly in the field of coordination chemistry. Compared with the traditional inorganic porous material, the material has the advantages of high porosity, large specific surface area, adjustability of the pore size of the framework, tailorability and diversity of the structure and the like, and has wide application in the fields of adsorption and separation, sensors, drug slow release, luminescence, catalysis and the like.
In recent years, electrospun nanofibers have been extensively studied by researchers in the adsorption field. Electrospinning, also known as electrospinning, is a process for producing polymeric microfibers by the action of a charged polymer solution or melt that is jetted in an electrostatic field. Due to the miniaturization of the size of the electrostatic spinning nanofiber material, the nanofiber material keeps the original chemical and physical properties, and meanwhile, the fiber membrane has large specific surface area, high porosity and good pore connectivity. The fiber membrane prepared by the electrospinning method has good biocompatibility and structural compatibility, and can be widely applied to biomedical materials. In addition, electrospun nanofibers are easily functionalized or readily available with specific beneficial structures to further improve adsorption capacity, making them more conducive to the removal of toxins from blood.
Normally, the kidney is the "sewage treatment plant" in the human body, which is responsible for the treatment of various toxins in the human body. Once the kidney becomes ill, the portion of the waste that the kidney is responsible for disposing of cannot be discharged from the body and is accumulated in the body, and the waste in the body is the toxin causing uremia, and the main purpose of hemodialysis is to remove the toxin. Among these numerous toxins, small molecule toxins have a relative molecular mass below 500, with the most typical toxins being primarily urea and creatinine. Cyanate, a metabolite of urea, is neurotoxic; creatinine reaches a certain concentration, which can cause cell life shortening, hemolysis, and abnormal neuromuscular system functions such as lethargy and asthenia. Therefore, the removal capacity of these two toxins is a fundamental requirement for investigating the performance of dialysis membranes. In the publication No. CN110026098A, a chitosan hemodialysis membrane is introduced, the prepared dialysis membrane has a urea removal rate of 87.1% and a protein retention rate of 96.7%, but the preparation process is complicated and creatinine removal is lacked. In the Chinese patent with publication number CN105709613A, a nanofiber composite membrane for removing medium biomolecules is introduced, the clearance rate of the prepared composite membrane to urea is 80-90%, the retention rate to protein is 98.5-9.5%, and the clearance to creatinine is lacked.
Based on the background, the invention firstly provides the MOFs modified double-layer structure composite electrospun nanofiber membrane, the preparation method thereof and the application thereof in blood purification. Firstly, preparing a polyacrylonitrile electrospun nanofiber membrane by utilizing an electrostatic spinning technology, and in order to overcome the problem of poor hydrophilicity of polyacrylonitrile, coating a layer of polydopamine on the surface of the polyacrylonitrile electrospun nanofiber membrane by utilizing the self-polymerization behavior of the dopamine so as to improve the hydrophilicity of the fiber and be more beneficial to the growth of MOFs on the surface of the fiber in the next step; in order to further improve the adsorption performance of the electrospun fiber membrane on urea in blood and grow Cu on the surface of the fiber membrane3(BTC)2Crystal particles; this film serves as the lower film. In addition, in order to improve the adsorption performance of the fibrous membrane on creatinine in blood and improve the biocompatibility of the fibrous membrane, the chitosan/sericin composite nanofiber membrane is prepared by using an electrostatic spinning technology and used as an upper membrane.This is reported to be the first use of MOFs-modified nanofiber membranes for blood purification. The electrospun nanofiber has good film forming property, good mechanical property, simple and easy preparation process and low cost, and has wide application prospect in the field of blood purification.
Disclosure of Invention
The invention aims to provide a MOFs modified double-layer structure composite electrospun nanofiber membrane, a preparation method thereof and application thereof in blood purification.
A MOFs modified double-layer structure composite electrospun nanofiber membrane is structurally characterized in that: the lower layer of the film takes polyacrylonitrile as a matrix, the surface of the fiber is coated with a layer of polydopamine, and Cu is regrown3(BTC)2Crystal particles, the film being an underlying film; the upper layer is a chitosan/sericin composite fiber film.
A preparation method of MOFs modified double-layer structure composite electrospun nanofiber membrane is characterized by comprising the following steps:
(1) dissolving polyacrylonitrile in a solvent N, N-dimethylformamide, and stirring until the polyacrylonitrile is completely dissolved, wherein the mass fraction of the polyacrylonitrile is 7-12 wt%;
(2) after the solution in the step (1) is completely dissolved to obtain a spinning solution, injecting the spinning solution into a spinning pipe for electrostatic spinning;
(3) drying the polyacrylonitrile electrospun nanofiber membrane obtained in the step (2), soaking the dried polyacrylonitrile electrospun nanofiber membrane with absolute ethyl alcohol, and heating and stirring the dried polyacrylonitrile electrospun nanofiber membrane in an aqueous solution with the pH of 8.5 and containing 3-6 mM dopamine;
(4) drying the polydopamine-coated electrospun nanofiber membrane obtained in the step (3), immersing the polydopamine-coated electrospun nanofiber membrane into 0.2-1.5M of copper nitrate water or ethanol solution for ultrasonic treatment and stirring, adding 0.1-0.4M of trimesic acid water or ethanol solution, and performing hydrothermal treatment to grow Cu on the surface of the polydopamine-coated electrospun nanofiber membrane3(BTC)2Crystal particles;
(5) dissolving chitosan and sericin in a mass ratio of 1: 1-5: 1 in trifluoroacetic acid as a solvent, and stirring until the chitosan and the sericin are completely dissolved, wherein the total mass fraction is 2-5 wt%;
(6) and (5) after the solution in the step (5) is completely dissolved to obtain a spinning solution, injecting the spinning solution into a spinning pipe for electrostatic spinning to obtain the chitosan/sericin electrospun fiber.
An application of a MOFs modified double-layer structure composite electrospun nanofiber membrane in blood purification is characterized in that: the obtained electrospun fiber membrane with the double-layer structure can effectively remove creatinine and urea in simulated blood and simultaneously retain protein, the removal rate of creatinine can reach 75-85%, the removal rate of urea can reach 75-85%, and the retention rate of bovine serum albumin can reach 95-99% after simulated dialysis.
The application of the MOFs modified double-layer structure composite electrospun nanofiber membrane in blood purification is characterized in that the nanofiber membrane is applied to a flat membrane dialyzer with a blood purification effect, and the flat membrane dialyzer with the blood purification effect comprises an upper dialysis chamber, a middle dialysis chamber and a lower dialysis chamber which are arranged in a stacked mode; both ends of each dialysis chamber are provided with a sample inlet and a sample outlet; and a dialysis membrane and a sealing gasket are clamped between the adjacent dialysis chambers, and the dialysis membrane is the MOFs modified double-layer structure composite electrospun nanofiber membrane.
The whole structure of the flat membrane dialyzer is cube-shaped, and the sizes of the dialysis chambers are 10-200 mm in length, 10-200 mm in width and 10-200 mm in height.
The filtering mode of the flat membrane is a dead-end filtering type or a cross-flow filtering type.
The upper dialysis chamber, the middle dialysis chamber and the lower dialysis chamber are fixedly locked through bolts at four corners.
The dialysis membrane includes but is not limited to a nano-fiber composite dialysis membrane, a polyether sulfone dialysis membrane, a polysulfone dialysis membrane, a polyacrylonitrile dialysis membrane, a polymethyl methacrylate dialysis membrane, a polyvinylidene fluoride dialysis membrane or a polylactic acid dialysis membrane
The method for testing the dialysis performance of the hemodialysis membrane comprises the following steps: and measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer according to the urea, creatinine and bovine serum albumin solutions with different concentrations, and drawing a standard curve by using measured data so as to determine the concentrations of the urea, the creatinine and the bovine serum albumin in the measured solution.
Has the advantages that:
(1) the invention uses N, N-dimethyl formamide as the solvent of spinning solution to prepare the electrospinning nano-fiber of polyacrylonitrile;
(2) according to the invention, the surface of the polyacrylonitrile fiber is coated with a layer of polydopamine, so that the hydrophilicity of the fiber membrane is improved, and the fiber membrane can be better applied to a water medium;
(3) cu grows uniformly on the surface of the lower fiber membrane of the MOFs modified double-layer structure composite electrospun nanofiber membrane3(BTC)2The crystal particles become rich adsorption sites, so that the adsorption capacity of the fiber membrane on urea is greatly improved;
(4) when the MOFs modified double-layer structure composite electrospun nanofiber membrane is used as a dialysis membrane, high protein retention rate can be achieved while urea and creatinine are effectively removed;
(5) the MOFs modified double-layer structure composite electrospun nanofiber membrane has the advantages of easily available raw materials, simplicity in operation, environmental friendliness, low cost and good application prospect.
(6) The flat membrane dialyzer designed and prepared by the invention can achieve the effect of removing small molecular and medium molecular toxins.
(7) The flat membrane dialyzer designed and prepared by the invention adopts the design of double dialysis chambers, so that two sides of blood to be dialyzed can be dialyzed simultaneously, and the dialysis efficiency is greatly improved.
(8) The flat membrane dialyzer designed and prepared by the invention has smaller size, is convenient to carry and operate, and is expected to improve the life quality of hemodialysis patients.
(9) The flat membrane dialyzer designed by the invention is easy to prepare, has simple process and is expected to realize industrial production.
Drawings
FIG. 1: scanning electron microscope photos of the lower layer film of the MOFs modified double-layer structure composite electrospun nanofiber membrane obtained in the embodiment 1;
FIG. 2: scanning electron microscope photos of the upper layer film of the MOFs modified double-layer structure composite electrospun nanofiber membrane obtained in the embodiment 1;
FIG. 3: schematic diagram of a flat membrane dialyzer.
Detailed Description
The present invention is further described below by way of examples, but the embodiments of the present invention are not limited thereto, and should not be construed as limiting the scope of the invention.
Example 1:
dissolving polyacrylonitrile in a solvent N, N-dimethylformamide, wherein the mass fraction of the polyacrylonitrile is 10 wt%, and heating and stirring at 50 ℃ until the polyacrylonitrile is completely dissolved; after the solution is completely dissolved, obtaining a spinning solution, and carrying out electrostatic spinning on the spinning solution; adding 200mg of dopamine into 100mL of tris (hydroxymethyl) aminomethane hydrochloride buffer solution with the pH value of 8.5, soaking the obtained electrostatic spinning nanofiber in ethanol, then putting the soaked electrostatic spinning nanofiber into the buffer solution, heating and stirring the solution at 45 ℃ for 24 hours, washing the solution with distilled water, and then drying the solution in a drying oven at 60 ℃ for overnight; soaking the obtained nanofiber membrane in 24mL of 0.5M copper nitrate solution with water and ethanol (the volume ratio of water to ethanol is 1:1) as solvents, performing ultrasonic treatment for 10min, stirring at room temperature for 1h, adding 24mL of 0.25M trimesic acid solution with water and ethanol (the volume ratio of water to ethanol is 1:1) as solvents, and performing hydrothermal reaction at 110 ℃ for 4 h; after the reaction is finished, the nanofiber membrane is cleaned by water and ethanol and then is placed in a 60 ℃ oven to be dried overnight, and a lower layer membrane is obtained. And dissolving chitosan and sericin in a trifluoroacetic acid solvent according to a mass ratio of 2.5:1, wherein the total mass fraction is 3 wt%, stirring at room temperature until the chitosan and the sericin are completely dissolved to obtain a spinning solution, and performing electrostatic spinning on the spinning solution to obtain an upper layer film.
The dialysis effect is obtained by removing solute and intercepting protein after dialysis membrane is dialyzed for 4 hours in a simulated mode, the simulated liquid is 1.5mg/mL urea, 0.1mg/mL creatinine and 1.0mg/mL bovine serum albumin solution, the dialysate is deionized water, the flow rate of the simulated liquid is 200mL/min, and the flow rate of the dialysate is 500 mL/min. The obtained MOFs modified double-layer structure composite electrospun nanofiber membrane has the creatinine clearance rate of 80%, the urea clearance rate of 80% and the bovine serum albumin retention rate of 98%.
Example 2:
dissolving polyacrylonitrile in a solvent N, N-dimethylformamide, wherein the mass fraction of the polyacrylonitrile is 8.5 wt%, and heating and stirring at room temperature until the polyacrylonitrile is completely dissolved; after the solution is completely dissolved, obtaining a spinning solution, and carrying out electrostatic spinning on the spinning solution; adding 160mg of dopamine into 80mL of tris (hydroxymethyl) aminomethane hydrochloride buffer solution with the pH value of 8.5, soaking the obtained electrostatic spinning nanofiber in ethanol, then putting the soaked electrostatic spinning nanofiber into the buffer solution, heating and stirring the solution at 45 ℃ for 24 hours, washing the solution with distilled water, and then drying the solution in a drying oven at 60 ℃ for overnight; soaking the obtained nanofiber membrane in 48mL of 0.8M copper nitrate ethanol solution, performing ultrasonic treatment for 10min, stirring at room temperature for 1h, adding 48mL of 0.4M trimesic acid ethanol solution, and slowly stirring at 50 ℃ for reaction for 2 h; after the reaction is finished, the nanofiber membrane is cleaned by ethanol and then is placed in a 60 ℃ oven to be dried overnight, and a lower layer membrane is obtained. And dissolving chitosan and sericin in a solvent trifluoroacetic acid according to a mass ratio of 3:1, wherein the total mass fraction is 3 wt%, stirring at room temperature until the chitosan and the sericin are completely dissolved to obtain a spinning solution, and performing electrostatic spinning on the spinning solution to obtain an upper layer film.
The dialysis effect is obtained by removing solute and intercepting protein after dialysis membrane is dialyzed for 4 hours in a simulated mode, the simulated liquid is 1.5mg/mL urea, 0.1mg/mL creatinine and 1.0mg/mL bovine serum albumin solution, the dialysate is deionized water, the flow rate of the simulated liquid is 200mL/min, and the flow rate of the dialysate is 500 mL/min. The obtained MOFs modified double-layer structure composite electrospun nanofiber membrane has the creatinine clearance rate of 78%, the urea clearance rate of 81% and the bovine serum albumin retention rate of 99%.
Example 3:
dissolving polyacrylonitrile in a solvent N, N-dimethylformamide, wherein the mass fraction of the polyacrylonitrile is 9 wt%, and heating and stirring at 70 ℃ until the polyacrylonitrile is completely dissolved; after the solution is completely dissolved, obtaining a spinning solution, and carrying out electrostatic spinning on the spinning solution; adding 200mg of dopamine into 100mL of tris (hydroxymethyl) aminomethane hydrochloride buffer solution with the pH value of 8.5, soaking the obtained electrostatic spinning nanofiber in ethanol, then putting the soaked electrostatic spinning nanofiber into the buffer solution, heating and stirring the solution at 45 ℃ for 24 hours, washing the solution with distilled water, and then drying the solution in a drying oven at 60 ℃ for overnight; soaking the obtained nanofiber membrane in 30mL of 0.7M copper nitrate solution, performing ultrasonic treatment for 10min, stirring at room temperature for 1h, adding 30mL of 0.35M trimesic acid ethanol solution, and performing hydrothermal reaction at 110 ℃ for 5 h; after the reaction is finished, the nanofiber membrane is cleaned by water and ethanol and then is placed in a 60 ℃ oven to be dried overnight, and a lower layer membrane is obtained. And dissolving chitosan and sericin in a solvent trifluoroacetic acid according to a mass ratio of 5:1, wherein the total mass fraction is 3 wt%, stirring at room temperature until the chitosan and the sericin are completely dissolved to obtain a spinning solution, and performing electrostatic spinning on the spinning solution to obtain an upper layer film.
The dialysis effect is obtained by removing solute and intercepting protein after dialysis membrane is dialyzed for 4 hours in a simulated mode, the simulated liquid is 1.5mg/mL urea, 0.1mg/mL creatinine and 1.0mg/mL bovine serum albumin solution, the dialysate is deionized water, the flow rate of the simulated liquid is 200mL/min, and the flow rate of the dialysate is 500 mL/min. The obtained MOFs modified double-layer structure composite electrospun nanofiber membrane has the removal rate of 82% on creatinine, 83% on urea and 98% on bovine serum albumin retention.
A simple flat membrane dialyzer with blood purification effect is further described below by way of specific examples, but the embodiments of the present invention are not limited thereto and should not be construed as limiting the scope of the present invention.
As shown in fig. 1, a schematic diagram of a simple flat membrane dialyzer with blood purification effect according to the present invention is shown, wherein the flat membrane dialyzer comprises an upper dialysis chamber 1, a middle dialysis chamber 2 and a lower dialysis chamber 3 which are stacked; the two ends of each dialysis chamber are respectively provided with a sample inlet 4 and a sample outlet 5; the adjacent dialysis chambers sandwich a dialysis membrane 6 and a sealing gasket 7.
The whole structure of the flat membrane dialyzer is cube-shaped, and the sizes of the dialysis chambers are 10-200 mm in length, 10-200 mm in width and 10-200 mm in height. The upper dialysis chamber 1, the middle dialysis chamber 2 and the lower dialysis chamber 3 are fixed and locked through bolts at four corners. The dialysis membrane 6 includes, but is not limited to, a nanofiber composite dialysis membrane, a polyethersulfone dialysis membrane, a polysulfone dialysis membrane, a polyacrylonitrile dialysis membrane, a polymethylmethacrylate dialysis membrane, a polyvinylidene fluoride dialysis membrane or a polylactic acid dialysis membrane.
During the installation, will dialyse membrane 6 and place between last dialysis room 1 and middle dialysis room 2 and lower dialysis room 3, in order to increase the steadiness of dialyse membrane 6, prevent the liquid seepage, use seal ring 7 fixed dialysis membrane 6, use four angles of each dialysis room together and lock with the bolt fastening at last. The sample inlet 4 and the sample outlet 5 at two ends of each dialysis chamber can be connected with a sample inlet pipe and a sample outlet pipe through an external connection tower street. The flat membrane dialyzer after being installed can be connected into a dialysis system to complete the hemodialysis process, so that the effect of removing small molecular and medium molecular toxins is achieved.
Claims (7)
1. A preparation method of MOFs modified double-layer structure composite electrospun nanofiber membrane is characterized by comprising the following steps:
(1) dissolving polyacrylonitrile in a solvent N, N-dimethylformamide, and stirring until the polyacrylonitrile is completely dissolved, wherein the mass fraction of the polyacrylonitrile is 7-12 wt%;
(2) after the solution in the step (1) is completely dissolved to obtain a spinning solution, injecting the spinning solution into a spinning pipe for electrostatic spinning;
(3) drying the polyacrylonitrile electrospun nanofiber membrane obtained in the step (2), soaking the dried polyacrylonitrile electrospun nanofiber membrane with absolute ethyl alcohol, and heating and stirring the dried polyacrylonitrile electrospun nanofiber membrane in an aqueous solution with the pH of 8.5 and containing 3-6 mM dopamine;
(4) drying the polydopamine-coated electrospun nanofiber membrane obtained in the step (3), immersing the polydopamine-coated electrospun nanofiber membrane into 0.2-1.5M of copper nitrate water or ethanol solution for ultrasonic treatment and stirring, adding 0.1-0.4M of trimesic acid water or ethanol solution, and performing hydrothermal treatment to grow Cu on the surface of the polydopamine-coated electrospun nanofiber membrane3(BTC)2Crystal particles;
(5) dissolving chitosan and sericin in a mass ratio of 1: 1-5: 1 in trifluoroacetic acid as a solvent, and stirring until the chitosan and the sericin are completely dissolved, wherein the total mass fraction is 2-5 wt%;
(6) and (5) after the solution in the step (5) is completely dissolved to obtain a spinning solution, injecting the spinning solution into a spinning pipe for electrostatic spinning to obtain the chitosan/sericin electrospun fiber.
2. The MOFs-modified double-layer structure composite electrospun nanofiber membrane obtained by the method according to claim 1, wherein the upper layer is a chitosan/sericin composite electrospun nanofiber membrane, and the lower layer is a MOFs-modified polyacrylonitrile nanofiber membrane.
3. The application of the MOFs modified double-layer structure composite electrospun nanofiber membrane in blood purification according to claim 2, wherein: the obtained electrospun fiber membrane with the double-layer structure can effectively remove creatinine and urea in simulated blood and simultaneously retain protein, the removal rate of creatinine can reach 75-85%, the removal rate of urea can reach 75-85%, and the retention rate of bovine serum albumin can reach 95-99% after simulated dialysis.
4. The application of the MOFs modified double-layer structure composite electrospun nanofiber membrane in blood purification according to claim 3, wherein: the nanofiber membrane is applied to a flat membrane dialyzer with a blood purification effect, and the flat membrane dialyzer with the blood purification effect comprises an upper dialysis chamber (1), a middle dialysis chamber (2) and a lower dialysis chamber (3) which are arranged in a stacked mode; both ends of each dialysis chamber are provided with a sample inlet (4) and a sample outlet (5); a dialysis membrane (6) and a sealing gasket (7) are clamped between the adjacent dialysis chambers, and the dialysis membrane (6) is the MOFs modified double-layer structure composite electrospun nanofiber membrane.
5. The application of the MOFs-modified double-layer structure composite electrospun nanofiber membrane in blood purification according to claim 4, wherein the whole structure of the flat membrane dialyzer is cubic, and the sizes of each dialysis chamber are 10-200 mm in length, 10-200 mm in width and 10-200 mm in height.
6. The use of the MOFs-modified double-layer structure composite electrospun nanofiber membrane according to claim 4, wherein the filtration mode of the flat sheet membrane is a dead-end filtration mode or a cross-flow filtration mode.
7. The application of the MOFs-modified double-layer structure composite electrospun nanofiber membrane according to claim 4, wherein the upper dialysis chamber (1), the middle dialysis chamber (2) and the lower dialysis chamber (3) are fixedly locked by bolts at four corners.
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