CN112175379B - Biological membrane material - Google Patents
Biological membrane material Download PDFInfo
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- CN112175379B CN112175379B CN202011062256.7A CN202011062256A CN112175379B CN 112175379 B CN112175379 B CN 112175379B CN 202011062256 A CN202011062256 A CN 202011062256A CN 112175379 B CN112175379 B CN 112175379B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
Abstract
The invention discloses a biological membrane material, which comprises the following raw materials: nano-scale silk fibroin powder, polyurethane, oxidized microcrystalline fiber/chitosan, silver nitrate, N-dimethylformamide, tetrahydrofuran and deionized water; the invention mixes the nano silk fibroin and medical polyurethane with good formability, and introduces the antibacterial active Ag by adding oxidized microcrystalline fiber/chitosan + The material is subjected to antibacterial functionalization to prepare the medical biomembrane, the nano-scale silk fibroin has smaller specific surface area and small steric hindrance, is more favorable for intermolecular combination, and the Ag is introduced + Reducing amino acids in the structure of post-fibroinThe residue has the capability of reducing metal ions, and Ag + The nano silver is reduced into a nano silver simple substance, and the nano silver simple substance is adsorbed or coated and distributed inside and outside a material matrix, so that the biological membrane prepared by the invention has the characteristics of good antibacterial effect, good forming effect and good biocompatibility.
Description
Technical Field
The invention belongs to the field of medical use, and particularly relates to a biological membrane material.
Background
Frequent nosocomial infection in hospitals is always a prominent problem to be solved urgently in clinical work, nosocomial infection not only affects reputation of hospitals and occupies a large amount of medical resources, but also brings unnecessary pain and burden to patients, and seriously threatens health and safety of human beings. Research has found that there are many pathogenic microorganisms causing nosocomial infections. The nosocomial infections mainly include bacterial infections, fungal infections, viral infections, protozoal infections, mycoplasma infections, chlamydial infections, etc., according to the types of pathogenic microorganisms, with bacterial infections being the most prevalent. Researches find that iatrogenic bacterial infection caused by the use of medical equipment field, medical materials and the like becomes an important way for nosocomial infection, for example, secondary materials such as novel artificial biomaterials, artificial organs, suction devices, artificial catheters, artificial venous catheters, monitoring instrument probes and the like have no antibacterial property, pathogenic microorganisms are easy to attach to the surfaces of the materials to grow and propagate, and local or whole body and mind infection is often caused. At present, the occurrence of nosocomial infection is mainly relieved by using a large amount of antibiotics in clinic, the use of the antibiotics is not only at the cost of damaging the health of human bodies, but also once the bacteria generate drug resistance, secondary or repeated infection is caused, and patients suffer more pain. Therefore, from the performance of the material, the research and development of the biological material with the antibacterial function have very important significance.
Disclosure of Invention
The invention aims to provide a biological membrane material.
The technical problems to be solved by the invention are as follows:
in the prior art, clinically used polyurethane, natural latex and the like have no antibacterial property, microorganisms are very easy to attach to the surfaces of the polyurethane, the natural latex and the like to grow, and the polyurethane, the natural latex and the like become the main culprit of nosocomial infection.
The purpose of the invention can be realized by the following technical scheme:
a biomembrane material comprises the following raw materials in parts by weight: 10-30 parts of nano-scale silk fibroin powder, 80-100 parts of polyurethane, 10-15 parts of oxidized microcrystalline fiber/chitosan, 3-5 parts of silver nitrate, 800-1000 parts of N, N-dimethylformamide, 100-200 parts of tetrahydrofuran and 1500-2000 parts of deionized water;
the preparation method of the biological membrane material comprises the following steps:
the method comprises the following steps of firstly, dividing N, N-dimethylformamide into 3 equal parts, and then respectively adding nanoscale silk fibroin powder, polyurethane and silver nitrate into the N, N-dimethylformamide to form nanoscale silk fibroin powder solution, polyurethane solution and silver nitrate solution;
secondly, adding a nano-scale silk fibroin powder solution and oxidized microcrystalline fiber/chitosan into a polyurethane solution, heating in a water bath at the temperature of 55-60 ℃, stirring at the rotating speed of 150-300r/min for 2-3h, then adding a silver nitrate solution, continuously reacting for 3-5h under the condition of unchanged temperature and rotating speed, adding 80% deionized water to separate out a reactant, then carrying out suction filtration, repeatedly washing with 20% deionized water, and drying at the temperature of 110-120 ℃ to constant weight to obtain a sheet-shaped antibacterial composite material;
and thirdly, adding the sheet antibacterial composite material obtained in the second step into tetrahydrofuran, stirring at the rotating speed of 100-200r/min for 30-50min to obtain a mixture, transferring the mixture into a film forming device by using a pipette, covering the top of the film forming device by using gauze, and standing for 16-24h to obtain the biomembrane material.
As a further aspect of this embodiment, the polyurethane is Texin5590, a german bayer aliphatic-medical grade polyurethane.
As a further scheme of the scheme, the preparation method of the nanoscale silk fibroin powder comprises the following steps:
s11, removing silkworm pupas from silkworm cocoon shells, shearing the silkworm cocoon shells into cocoon shell segments of 1-2cm, washing the cocoon shell segments for 3-5 times by using deionized water, and airing the cocoon shell segments for later use;
step S12, soaking the cocoon shell treated in the step S11 in ethyl ether for 36-48h to remove waxy substances on the surface of the cocoon shell, stirring the cocoon shell for 1 time by using a glass rod every 3h during soaking, replacing the ethyl ether once for 12h, then filtering, washing filter residues for three times by using deionized water, airing to obtain a wax-removed cocoon shell, soaking the wax-removed cocoon shell in an absolute ethyl alcohol solution for 24h to remove carbohydrates and ash in the cocoon shell, filtering, washing the filter residues for 3-5 times by using the deionized water, then drying in a drying oven at 50-60 ℃ for 5-10h to obtain a dry and carbohydrate-removed silkworm shell, placing the dry and carbohydrate-removed silkworm shell in the deionized water according to a bath ratio of 1;
s13, putting the coarse silk fibroin into prepared Na with the mass fraction of 0.4% according to the bath ratio of 1 2 CO 3 Boiling the solution for 2-3h, changing the solution every 0.5h, cooling to room temperature, vacuum filtering, removing filtrate, washing the filter residue with distilled water for three times, and drying in an oven at 50-55 deg.C to constant weight to obtain refined fibroin fiber;
step S14, adding CaCl 2 、C 2 H 5 OH and distilled water are mixed according to a molar ratio of 1-3;
s15, filling a silk fibroin salt solution into a dialysis bag, putting the dialysis bag into distilled water for dialysis for 3-5 days, changing the distilled water every 12 hours, and after the dialysis is finished, transferring a mixture in the dialysis bag into a beaker to obtain a silk fibroin solution;
s16, placing the silk fibroin solution in a water bath thermostat at 54-58 ℃ for 10-20min in a water bath, adjusting the pH value of the silk fibroin solution to 6.0-7.0 by using an ammonia water solution with the mass fraction of 25%, adding neutral protease according to the mass ratio of 1;
and S17, pouring the nano-scale silk fibroin solution into a round-bottom flask, mounting the round-bottom flask on a rotary evaporator for concentration, stopping concentration when the volume of the solution is 1/3, pre-freezing the nano-scale silk fibroin concentrated solution in an ultra-low temperature refrigerator at-70 ℃ for 12 hours, and then carrying out vacuum drying at-110 ℃ for 36 hours to obtain nano-scale silk fibroin powder.
As a further scheme of the scheme, the using ratio of the cocoon shell, the diethyl ether and the absolute ethyl alcohol solution in the step S12 is 1g:20-30 mL; the enzyme activity of the neutral protease in the step S16 is 20 ten thousand mu/g.
As a further scheme of the scheme, the preparation method of the oxidized microcrystalline fiber/chitosan comprises the following steps:
step S21, naIO 4 Adding into deionized water, adding sulfuric acid solution with mass fraction of 30-40%, adjusting pH value of the solution to 4-5, adding microcrystalline cellulose into the solution, stirring at a rotation speed of 200-300r/min for 2-3h in the dark condition, suction filtering, washing filter residue with distilled water for 3-5 times, and drying in an oven at 110-120 deg.C to constant weight to obtain oxidized microcrystalline fiber;
step S22, adding chitosan with the molecular weight of 80-100 ten thousand into acetic acid solution with the mass fraction of 3-5%, and magnetically stirring for 20-40min at the temperature of 60-65 ℃ to obtain chitosan dispersion liquid;
step S23, adding oxidized microcrystalline fibers into deionized water, controlling the temperature to be 40-50 ℃, filling nitrogen to remove oxygen for 30min, stirring for 20-30min under the condition of the rotating speed of 100-200r/min, then adding EDC and NHS composite coupling agent with the mass ratio of 1-3, and stirring for 30-50min under the condition of the rotating speed unchanged to obtain oxidized microcrystalline fiber treatment liquid;
and S24, dropwise adding the chitosan dispersion liquid obtained in the step S22 into the oxidized microcrystalline fiber treatment liquid, stirring at the rotating speed of 200-300r/min for 15-20h, then adding a NaOH solution with the mass fraction of 2%, making the solution neutral and generating floccules, performing suction filtration, washing filter residues with deionized water for 5-10 times, and drying at the temperature of 100-110 ℃ to constant weight to obtain the oxidized microcrystalline fiber/chitosan.
As a further scheme of the scheme, the microcrystalline cellulose and NaIO in the step S21 4 The mass ratio of the chitosan to the acetic acid solution with the mass fraction of 3-5% in the step S22 is 1g:10-20mL, and the dosage ratio of the oxidized microcrystalline fiber, the deionized water and the EDC and NHS composite coupling agent in the step S231g:20-30mL:0.1-05g; in step S24, the volume ratio of the oxidized microcrystalline fiber treatment solution to the chitosan dispersion solution is 1:1-3.
The invention has the beneficial effects that:
1. the invention mixes the nano silk fibroin and medical polyurethane with good formability, and introduces the antibacterial active Ag by adding oxidized microcrystalline fiber/chitosan + The silk fibroin fiber of silkworm shell is subjected to salt dissolution, dialysis, enzymolysis, freeze drying and other processes to prepare powdery nano silk fibroin to ensure that the powdery nano silk fibroin has the characteristics of the nano material, the excellent characteristics of all aspects can be fully reflected, the polar group of the silk fibroin is fully exposed in the enzymolysis process to be more favorable for the combination of the silk fibroin, polyurethane, oxidized microcrystalline fiber/chitosan, and-NH of the nano silk fibroin 3 Polar groups such as-COOH, -OH and the like are combined with groups such as-NHC 00 and the like of polyurethane through molecular actions such as hydrogen bonds, van der Waals force and the like, the nano-scale silk fibroin has smaller specific surface area and small steric hindrance, is more favorable for intermolecular combination, and Ag is introduced + The reducing amino acid residue in the structure of the post-silk fibroin has the capability of reducing metal ions, and Ag is removed + The nano silver is reduced into a nano silver simple substance, and the nano silver simple substance is adsorbed or coated and distributed inside and outside a material matrix, so that the biological membrane prepared by the invention has the characteristics of good antibacterial effect, good forming effect and good biocompatibility.
2. Chitosan makes a linear and semi-crystalline alkaline natural polysaccharide polymer, which has good biocompatibility and biodegradability, nontoxicity and antibacterial property, and provides a proper warm and humid environment for wound healing, oxidized microcrystalline fiber is a polymer material, and has the excellent characteristics of nontoxicity, biocompatibility, biodegradability, timely hemostasis and the like, EDC and NHS are coupling agents with non-toxicity and good biological properties, EDC is active in chemical property and can form amido bond between amino and carboxyl, EDC reacts with carboxyl of a compound to form an O-amide urea intermediate capable of reacting with amino, and the O-amide urea intermediate can be converted into NHS ester with amino reaction activity in the presence of NHS, so that EDC-mediated condensation reaction efficiency is greatly improved, and grafting yield is improved. According to the invention, chitosan and oxidized microcrystalline cellulose are grafted through coupling agents EDC and NHS, so that the chitosan and the oxidized cellulose are modified mutually, the performance of a single raw material is improved, and more excellent biological filler is obtained.
3. The biological membrane combines the biocompatibility of silk fibroin, the molding processability of polyurethane, the cooperativity of oxidized microcrystalline fiber/chitosan, and the addition of silver endows the biological membrane with wide antibacterial property, can be used as a raw material of a medical catheter, a coating of medical equipment and other biomedical materials, reduces or alleviates the occurrence of hospital iatrogenic infection, reduces the use of antibiotics, and is beneficial to reducing the pain of patients
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A biomembrane material comprises the following raw materials in parts by weight: 10 parts of nano-scale silk fibroin powder, 80 parts of polyurethane, 10 parts of oxidized microcrystalline fiber/chitosan, 3 parts of silver nitrate, 800 parts of N, N-dimethylformamide, 100 parts of tetrahydrofuran and 1500 parts of deionized water;
the preparation method of the biological membrane material comprises the following steps:
the method comprises the following steps of firstly, dividing N, N-dimethylformamide into 3 equal parts, and then respectively adding nanoscale silk fibroin powder, polyurethane and silver nitrate into the N, N-dimethylformamide to form nanoscale silk fibroin powder solution, polyurethane solution and silver nitrate solution;
secondly, adding a nano-scale silk fibroin powder solution and oxidized microcrystalline fiber/chitosan into a polyurethane solution, heating in a water bath at 55 ℃, stirring at a rotation speed of 150r/min for 2h, then adding a silver nitrate solution, continuously reacting for 3h under the conditions of constant temperature and rotation speed, adding 80% deionized water to separate out a reactant, then performing suction filtration, repeatedly washing with 20% deionized water, and drying at 110 ℃ to constant weight to obtain a sheet-shaped antibacterial composite material;
and thirdly, adding the sheet antibacterial composite material obtained in the second step into tetrahydrofuran, stirring at the rotating speed of 100r/min for 30min to obtain a mixture, transferring the mixture into a film forming device by using a pipette, covering the top of the film forming device by using gauze, and standing for 16h to obtain the biomembrane material.
The polyurethane is German Bayer aliphatic-medical grade polyurethane Texin5590.
The preparation method of the nano-scale silk fibroin powder comprises the following steps:
s11, removing silkworm pupas from silkworm cocoon shells, shearing the silkworm cocoon shells into cocoon shell segments of 1cm, washing the cocoon shell segments for 3 times by using deionized water, and airing the cocoon shell segments for later use;
step S12, placing the cocoon shell treated in the step S11 into ether to be soaked for 36h to remove waxy substances on the surface of the cocoon shell, stirring 1 time by using a glass rod every 3h during soaking, replacing ether once every 12h, then filtering, washing filter residue three times by using deionized water, airing to obtain a wax-removed cocoon shell, placing the wax-removed cocoon shell into an absolute ethyl alcohol solution to be soaked for 24h, removing carbohydrate and ash in the cocoon shell, filtering, washing the filter residue 3 times by using the deionized water, then placing the cocoon shell into a 50 ℃ drying oven to be dried for 5h to obtain a dried carbohydrate-removed silkworm shell, placing the dried carbohydrate-removed silkworm shell into the deionized water according to a bath ratio of 1;
s13, putting the coarse silk fibroin into prepared Na with the mass fraction of 0.4% according to the bath ratio of 1 2 CO 3 Boiling the solution for 2h, changing the solution every 0.5h, cooling to room temperature, filtering, removing filtrate, washing the filter residue with distilled water for three times, and drying in a 50 ℃ oven to constant weight to obtain refined fibroin fiber;
step S14, adding CaCl 2 、C 2 H 5 OH and distilled water are mixed according to a molar ratio of 1A fibroin salt solution;
s15, filling a silk fibroin salt solution into a dialysis bag, putting the dialysis bag into distilled water for dialysis for 3 days, changing the distilled water every 12 hours, and after the dialysis is finished, transferring the mixture in the dialysis bag into a beaker to obtain a silk fibroin solution;
s16, placing the silk fibroin solution in a water bath thermostat at 54 ℃ for 10min, adjusting the pH value of the silk fibroin solution to 6.0 by using an ammonia water solution with the mass fraction of 25%, adding neutral protease according to the mass ratio of 1;
and S17, pouring the nano-scale silk fibroin solution into a round-bottom flask, placing the round-bottom flask on a rotary evaporator for concentration, stopping concentration when the volume of the solution is 1/3, placing the nano-scale silk fibroin concentrated solution in an ultra-low temperature refrigerator at minus 70 ℃ for pre-freezing for 12 hours, and then carrying out vacuum drying for 36 hours at minus 110 ℃ to obtain nano-scale silk fibroin powder.
The using amount ratio of the cocoon shell, the diethyl ether and the absolute ethyl alcohol solution in the step S12 is 1g:20 mL; the enzyme activity of the neutral protease in the step S16 is 20 ten thousand mu/g.
The preparation method of the oxidized microcrystalline fiber/chitosan comprises the following steps:
step S21, adding NaIO 4 Adding the mixture into deionized water, adding a sulfuric acid solution with the mass fraction of 30%, adjusting the pH value of the solution to 4, adding microcrystalline cellulose into the solution, stirring at the rotating speed of 200r/min for 2 hours in the dark condition, then performing suction filtration, washing filter residues with distilled water for 3 times, and drying in an oven at the temperature of 110 ℃ to constant weight to obtain oxidized microcrystalline fiber;
s22, adding 80-ten-thousand-molecular-weight chitosan into an acetic acid solution with the mass fraction of 3%, and magnetically stirring at the temperature of 60 ℃ for 20min to obtain a chitosan dispersion liquid;
s23, adding oxidized microcrystalline fibers into deionized water, controlling the temperature at 40 ℃, filling nitrogen to remove oxygen for 30min, stirring for 20min at the rotating speed of 100r/min, adding an EDC and NHS composite coupling agent with the mass ratio of 1, and stirring for 30min at the rotating speed of unchanged to obtain an oxidized microcrystalline fiber treatment solution;
and S24, dropwise adding the chitosan dispersion liquid obtained in the step S22 into the oxidized microcrystalline fiber treatment liquid, stirring at a rotating speed of 200r/min for 15 hours, then adding a NaOH solution with the mass fraction of 2% to enable the solution to be neutral and generate floccules, carrying out suction filtration, washing filter residues with deionized water for 5 times, and drying at 100 ℃ to constant weight to obtain the oxidized microcrystalline fiber/chitosan.
Microcrystalline cellulose and NaIO in step S21 4 The mass ratio of the chitosan to the 3-5% acetic acid solution in the step S22 is 1g:10mL, wherein the dosage ratio of the oxidized microcrystalline fibers, the deionized water and the EDC and NHS composite coupling agent in the step S23 is 1g:20mL of: 0.1g; in step S24, the volume ratio of the oxidized microcrystalline fiber treatment solution to the chitosan dispersion solution is 1:1.
example 2
A biomembrane material comprises the following raw materials in parts by weight: 20 parts of nano-scale silk fibroin powder, 90 parts of polyurethane, 12 parts of oxidized microcrystalline fiber/chitosan, 4 parts of silver nitrate, 900 parts of N, N-dimethylformamide, 150 parts of tetrahydrofuran and 1800 parts of deionized water;
the preparation method of the biological membrane material comprises the following steps:
the method comprises the following steps of firstly, dividing N, N-dimethylformamide into 3 equal parts, and then respectively adding nanoscale silk fibroin powder, polyurethane and silver nitrate into the N, N-dimethylformamide to form nanoscale silk fibroin powder solution, polyurethane solution and silver nitrate solution;
secondly, adding a nanoscale silk fibroin powder solution and oxidized microcrystalline fiber/chitosan into a polyurethane solution, heating in a water bath at the temperature of 58 ℃, stirring for 2.5 hours at the rotation speed of 200r/min, then adding a silver nitrate solution, continuously reacting for 4 hours under the conditions of constant temperature and rotation speed, adding 80% deionized water to separate out a reactant, then performing suction filtration, repeatedly washing with 20% deionized water, and drying at the temperature of 115 ℃ to constant weight to obtain a sheet-shaped antibacterial composite material;
and thirdly, adding the sheet-shaped antibacterial composite material obtained in the second step into tetrahydrofuran, stirring at the rotating speed of 150r/min for 40min to obtain a mixture, transferring the mixture into a film forming device by using a pipette, covering the top of the film forming device by using gauze, and standing for 20h to obtain the biofilm material.
The polyurethane is German Bayer aliphatic-medical grade polyurethane Texin5590.
The preparation method of the nano-scale silk fibroin powder comprises the following steps:
s11, removing silkworm pupas from silkworm cocoon shells, shearing the silkworm cocoon shells into cocoon shell segments of 1.5cm, washing the cocoon shell segments for 4 times by using deionized water, and airing the cocoon shells for later use;
step S12, placing the cocoon shell treated in the step S11 into ether to be soaked for 45 hours to remove waxy substances on the surface of the cocoon shell, stirring the cocoon shell for 1 time by using a glass rod every 3 hours during soaking, replacing the ether once every 12 hours, then filtering, washing filter residue for three times by using deionized water, airing to obtain a wax-removed cocoon shell, placing the wax-removed cocoon shell into an absolute ethyl alcohol solution to be soaked for 24 hours, removing carbohydrates and ash in the cocoon shell, filtering, washing the filter residue for 4 times by using the deionized water, then placing the cocoon shell into an oven at 55 ℃ to be dried for 8 hours to obtain a dried carbohydrate-removed silkworm shell, placing the dried carbohydrate-removed silkworm shell into the deionized water according to a bath ratio of 1;
s13, putting the coarse silk fibroin into prepared Na with the mass fraction of 0.4% according to the bath ratio of 1 2 CO 3 Boiling the solution for 2.5h, changing the solution every 0.5h, cooling to room temperature, vacuum filtering, removing filtrate, washing the filter residue with distilled water for three times, and drying in an oven at 53 deg.C to constant weight to obtain refined fibroin fiber;
step S14, adding CaCl 2 、C 2 H 5 OH and distilled water are mixed according to a molar ratio of 1.5;
s15, filling a silk fibroin salt solution into a dialysis bag, putting the dialysis bag into distilled water for dialysis for 4 days, changing the distilled water every 12 hours, and transferring the mixture in the dialysis bag into a beaker after the dialysis is finished to obtain a silk fibroin solution;
s16, placing the silk fibroin solution in a water bath thermostat at 56 ℃ for 15min, adjusting the pH value of the silk fibroin solution to 6.5 by using an ammonia water solution with the mass fraction of 25%, adding neutral protease according to the mass ratio of the neutral protease to the silk fibroin solution of 1:13, stirring for 1.5h at the rotation speed of 80r/min, cooling to room temperature, and filtering by using an ultrafiltration membrane with the enzyme-removing aperture of 0.22 mu m to obtain a nano-scale silk fibroin solution;
and S17, pouring the nano-scale silk fibroin solution into a round-bottom flask, mounting the round-bottom flask on a rotary evaporator for concentration, stopping concentration when the volume of the solution is 1/3, pre-freezing the nano-scale silk fibroin concentrated solution in an ultra-low temperature refrigerator at-70 ℃ for 12 hours, and then carrying out vacuum drying at-110 ℃ for 36 hours to obtain nano-scale silk fibroin powder.
The dosage ratio of the cocoon shell, the ether and the absolute ethyl alcohol solution in the step S12 is 1g:25 mL; the enzyme activity of the neutral protease in the step S16 is 20 ten thousand mu/g.
The preparation method of the oxidized microcrystalline fiber/chitosan comprises the following steps:
step S21, adding NaIO 4 Adding into deionized water, adding 35 wt% sulfuric acid solution, adjusting pH to 4.5, adding microcrystalline cellulose into the solution, stirring at 250r/min for 2.5h in the dark, vacuum filtering, washing the filter residue with distilled water for 4 times, and drying in an oven at 115 deg.C to constant weight to obtain oxidized microcrystalline fiber;
step S22, adding chitosan with the molecular weight of 90 ten thousand into acetic acid solution with the mass fraction of 4%, and magnetically stirring for 30min at the temperature of 63 ℃ to obtain chitosan dispersion liquid;
step S23, adding oxidized microcrystalline fibers into deionized water, controlling the temperature at 43 ℃, filling nitrogen to remove oxygen for 30min, stirring for 25min under the condition of a rotation speed of 150r/min, adding an EDC and NHS composite coupling agent with a mass ratio of 2, and stirring for 40min under the condition of a constant rotation speed to obtain an oxidized microcrystalline fiber treatment solution;
and S24, dropwise adding the chitosan dispersion liquid obtained in the step S22 into the oxidized microcrystalline fiber treatment liquid, stirring at the rotating speed of 250r/min for 18h, then adding a NaOH solution with the mass fraction of 2% to make the solution neutral and generate floccules, carrying out suction filtration, washing filter residues with deionized water for 8 times, and drying at 105 ℃ to constant weight to obtain the oxidized microcrystalline fiber/chitosan.
Microcrystalline cellulose and NaIO in step S21 4 The mass ratio of the chitosan to the acetic acid solution with the mass fraction of 4% in the step S22 is 1g:15mL, wherein the dosage ratio of the oxidized microcrystalline fibers, the deionized water and the EDC and NHS composite coupling agent in the step S23 is 1g:25mL of: 0.4g; in step S24, the volume ratio of the oxidized microcrystalline fiber treatment solution to the chitosan dispersion solution is 1:2.
example 3
A biomembrane material comprises the following raw materials in parts by weight: 30 parts of nano-scale silk fibroin powder, 100 parts of polyurethane, 15 parts of oxidized microcrystalline fiber/chitosan, 5 parts of silver nitrate, 1000 parts of N, N-dimethylformamide, 200 parts of tetrahydrofuran and 2000 parts of deionized water;
the preparation method of the biological membrane material comprises the following steps:
the method comprises the following steps of firstly, dividing N, N-dimethylformamide into 3 equal parts, and then respectively adding nanoscale silk fibroin powder, polyurethane and silver nitrate into the N, N-dimethylformamide to form nanoscale silk fibroin powder solution, polyurethane solution and silver nitrate solution;
secondly, adding a nanoscale silk fibroin powder solution and oxidized microcrystalline fiber/chitosan into a polyurethane solution, heating in a water bath at the temperature of 60 ℃, stirring for 3 hours at the rotation speed of 300r/min, then adding a silver nitrate solution, continuously reacting for 5 hours under the conditions of constant temperature and rotation speed, adding 80% deionized water to separate out a reactant, then performing suction filtration, repeatedly washing with 20% deionized water, and drying at the temperature of 120 ℃ to constant weight to obtain a sheet-shaped antibacterial composite material;
and thirdly, adding the sheet-shaped antibacterial composite material obtained in the second step into tetrahydrofuran, stirring at the rotating speed of 200r/min for 50min to obtain a mixture, transferring the mixture into a film forming device by using a pipette, covering the top of the film forming device by using gauze, and standing for 24h to obtain the biofilm material.
The polyurethane is German Bayer aliphatic-medical grade polyurethane Texin5590.
The preparation method of the nano-scale silk fibroin powder comprises the following steps:
s11, removing silkworm pupas from silkworm cocoon shells, shearing the silkworm cocoon shells into cocoon shell segments of 2cm, washing the cocoon shell segments for 5 times by using deionized water, and airing the cocoon shell segments for later use;
step S12, placing the cocoon shell treated in the step S11 into ether to be soaked for 48 hours to remove waxy substances on the surface of the cocoon shell, stirring the cocoon shell for 1 time by using a glass rod every 3 hours during soaking, replacing ether once for 12 hours, then filtering, washing filter residue for three times by using deionized water, airing to obtain a wax-removed cocoon shell, placing the wax-removed cocoon shell into an absolute ethyl alcohol solution to be soaked for 24 hours, removing carbohydrates and ash in the cocoon shell, filtering, washing the filter residue for 5 times by using the deionized water, then placing the cocoon shell into a 60 ℃ drying oven to be dried for 10 hours to obtain a dried carbohydrate-removed silkworm shell, placing the dried carbohydrate-removed silkworm shell into the deionized water according to a bath ratio of 1;
step S13, placing the coarse silk fibroin fibers into prepared Na with the mass fraction of 0.4% according to a bath ratio of 1 2 CO 3 Boiling the solution for 3h, changing the solution every 0.5h, cooling to room temperature, filtering, removing filtrate, washing the filter residue with distilled water for three times, and drying in an oven at 55 deg.C to constant weight to obtain refined fibroin fiber;
step S14, adding CaCl 2 、C 2 H 5 OH and distilled water are mixed according to a molar ratio of 1;
s15, filling a silk fibroin salt solution into a dialysis bag, putting the dialysis bag into distilled water for dialysis for 5 days, changing the distilled water every 12 hours, and transferring the mixture in the dialysis bag into a beaker after the dialysis is finished to obtain a silk fibroin solution;
s16, placing the silk fibroin solution in a water bath thermostat at 58 ℃ for 20min in a water bath, adjusting the pH value of the silk fibroin solution to 7.0 by using an ammonia water solution with the mass fraction of 25%, adding neutral protease according to the mass ratio of the neutral protease to the silk fibroin solution of 115, stirring for 2h at the rotation speed of 100r/min, cooling to room temperature, and filtering by using an ultrafiltration membrane with the enzyme-removing aperture of 0.22 mu m to obtain a nanoscale silk fibroin solution;
and S17, pouring the nano-scale silk fibroin solution into a round-bottom flask, mounting the round-bottom flask on a rotary evaporator for concentration, stopping concentration when the volume of the solution is 1/3, pre-freezing the nano-scale silk fibroin concentrated solution in an ultra-low temperature refrigerator at-70 ℃ for 12 hours, and then carrying out vacuum drying at-110 ℃ for 36 hours to obtain nano-scale silk fibroin powder.
The dosage ratio of the cocoon shells, the diethyl ether and the absolute ethyl alcohol solution in the step S12 is 1g:30 mL; the enzyme activity of the neutral protease in the step S16 is 20 ten thousand mu/g.
The preparation method of the oxidized microcrystalline fiber/chitosan comprises the following steps:
step S21, adding NaIO 4 Adding the mixture into deionized water, adding a sulfuric acid solution with the mass fraction of 40%, adjusting the pH value of the solution to be 5, adding microcrystalline cellulose into the solution, stirring for 3 hours at the rotating speed of 300r/min in the dark condition, then performing suction filtration, washing filter residues with distilled water for 5 times, and drying in an oven at the temperature of 120 ℃ to constant weight to obtain oxidized microcrystalline fibers;
step S22, adding chitosan with the molecular weight of 100 ten thousand into an acetic acid solution with the mass fraction of 5%, and magnetically stirring for 40min at the temperature of 65 ℃ to obtain chitosan dispersion liquid;
s23, adding oxidized microcrystalline fibers into deionized water, controlling the temperature at 50 ℃, filling nitrogen to remove oxygen for 30min, stirring for 30min at the rotation speed of 200r/min, adding an EDC and NHS composite coupling agent with the mass ratio of 3;
and S24, dropwise adding the chitosan dispersion liquid obtained in the step S22 into the oxidized microcrystalline fiber treatment liquid, stirring at the rotating speed of 300r/min for 20 hours, then adding a NaOH solution with the mass fraction of 2% to enable the solution to be neutral and generate floccules, performing suction filtration, washing filter residues for 10 times by using deionized water, and drying at 110 ℃ to constant weight to obtain the oxidized microcrystalline fiber/chitosan.
The microcrystalline fiber obtained in step S21Vitamin and NaIO 4 The mass ratio of the chitosan to the acetic acid solution with the mass fraction of 5% in the step S22 is 1g:20mL, wherein the dosage ratio of the oxidized microcrystalline fibers, the deionized water and the EDC and NHS composite coupling agent in the step S23 is 1g:30mL of: 05g of the total weight of the mixture; in step S24, the volume ratio of the oxidized microcrystalline fiber treatment solution to the chitosan dispersion solution is 1:3.
comparative example
The comparative example is a common biological membrane material in the market.
The biomembrane materials of examples 1-3 and comparative examples were subjected to mechanical property tests, mainly for elastic modulus, elongation at break, tensile strength, antibacterial property and platelet adhesion tests, the specific test method of platelet adhesion test was: cutting the membranes of examples 1-3 and comparative examples into disks with a diameter of 0.5cm, placing 0.1g of the prepared small disk membrane samples into test tubes, adding 1mL of fresh anticoagulated rabbit blood, placing in a 37 ℃ constant temperature water bath oscillator, oscillating to make the blood fully contact with the membrane material, keeping for 1h, adding 19mL3.8% sodium citrate solution, standing for 2h after reverse mixing, collecting the supernatant, and performing platelet counting under a biological inverted microscope to obtain the platelet consumption rate (P) c ) Calculated as follows: p C =（N 0 -N t ）/N 0 X 100%, wherein N 0 Indicates the number of platelets before contact, N t The number of platelets after contact is indicated. The test results were as follows:
as can be seen from the above table, the mechanical property test of the biological membrane prepared in the examples 1-3 is far better than that of the comparative example, the antibacterial property is also better than that of the comparative example, the platelet consumption rate is 28.7-30.6%, which is less than 40% of the biological safety requirement, and the platelet consumption rate of the comparative example is more than 40%, which indicates that the biological membrane material prepared by the invention has good mechanical property, antibacterial property and biocompatibility.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. The biological membrane material is characterized by comprising the following raw materials in parts by weight: 10-30 parts of nano-scale silk fibroin powder, 80-100 parts of polyurethane, 10-15 parts of oxidized microcrystalline fiber/chitosan, 3-5 parts of silver nitrate, 800-1000 parts of N, N-dimethylformamide, 100-200 parts of tetrahydrofuran and 1500-2000 parts of deionized water;
the preparation method of the biological membrane material comprises the following steps:
the method comprises the following steps of firstly, dividing N, N-dimethylformamide into 3 equal parts, and respectively adding nanoscale silk fibroin powder, polyurethane and silver nitrate into the N, N-dimethylformamide to form nanoscale silk fibroin powder solution, polyurethane solution and silver nitrate solution;
secondly, adding a nano-scale silk fibroin powder solution and oxidized microcrystalline fiber/chitosan into a polyurethane solution, heating in a water bath at the temperature of 55-60 ℃, stirring at the rotating speed of 150-300r/min for 2-3h, then adding a silver nitrate solution, continuously reacting for 3-5h under the condition of unchanged temperature and rotating speed, adding 80% deionized water to separate out a reactant, then carrying out suction filtration, repeatedly washing with 20% deionized water, and drying at the temperature of 110-120 ℃ to constant weight to obtain a sheet-shaped antibacterial composite material;
thirdly, adding the sheet-shaped antibacterial composite material obtained in the second step into tetrahydrofuran, stirring at the rotating speed of 100-200r/min for 30-50min to obtain a mixture, transferring the mixture into a film forming device by using a pipette, covering the top of the film forming device by using gauze, and standing for 16-24h to obtain a biological film material;
the preparation method of the oxidized microcrystalline fiber/chitosan comprises the following steps:
step S21, adding NaIO 4 Adding into deionized water, adding 30-40 wt% sulfuric acid solution, adjusting pH to 4-5, adding microcrystalline cellulose, and stirring at 200-300r/min for 2-3 hr in dark conditionThen carrying out suction filtration, washing filter residues with distilled water for 3-5 times, and drying in an oven at 110-120 ℃ to constant weight to obtain oxidized microcrystalline fibers;
step S22, adding chitosan with the molecular weight of 80-100 ten thousand into acetic acid solution with the mass fraction of 3-5%, and magnetically stirring for 20-40min at the temperature of 60-65 ℃ to obtain chitosan dispersion liquid;
s23, adding oxidized microcrystalline fibers into deionized water, controlling the temperature to be 40-50 ℃, filling nitrogen to remove oxygen for 30min, stirring for 20-30min under the condition of the rotating speed of 100-200r/min, adding EDC and NHS composite coupling agent with the mass ratio of 1-3, and stirring for 30-50min under the condition of the rotating speed unchanged to obtain oxidized microcrystalline fiber treatment solution;
and S24, dropwise adding the chitosan dispersion liquid obtained in the step S22 into the oxidized microcrystalline fiber treatment liquid, stirring at the rotating speed of 200-300r/min for 15-20h, then adding a NaOH solution with the mass fraction of 2%, making the solution neutral and generating floccules, carrying out suction filtration, washing filter residues with deionized water for 5-10 times, and drying at 100-110 ℃ to constant weight to obtain the oxidized microcrystalline fiber/chitosan.
2. The biofilm material as claimed in claim 1, wherein said polyurethane is Texin5590, german bayer aliphatics-medical grade polyurethane.
3. The biofilm material as claimed in claim 1, wherein the preparation method of the nanoscale silk fibroin powder comprises the following steps:
s11, removing silkworm pupas from silkworm cocoon shells, shearing the silkworm cocoon shells into cocoon shell segments of 1-2cm, washing the cocoon shell segments for 3-5 times by using deionized water, and airing the cocoon shell segments for later use;
step S12, placing the cocoon shells processed in the step S11 into ethyl ether to be soaked for 36-48h, stirring 1 time by using a glass rod every 3h during soaking, replacing ethyl ether once every 12h, then filtering, washing filter residues with deionized water for three times, airing to obtain paraffin-removed cocoon shells, placing the paraffin-removed cocoon shells into an absolute ethyl alcohol solution to be soaked for 24h, then filtering, washing the filter residues with deionized water for 3-5 times, then placing the filter residues into a drying oven at 50-60 ℃ to be dried for 5-10h to obtain dry carbohydrate-removed cocoon shells, placing the dry carbohydrate-removed cocoon shells into deionized water according to a bath ratio of 1;
s13, putting the coarse silk fibroin into prepared Na with the mass fraction of 0.4% according to the bath ratio of 1 2 CO 3 Boiling the solution for 2-3h, changing the solution every 0.5h, cooling to room temperature, filtering, removing filtrate, washing the filter residue with distilled water for three times, and drying in an oven at 50-55 deg.C to constant weight to obtain refined fibroin fiber;
step S14, adding CaCl 2 、C 2 H 5 OH and distilled water are mixed according to a molar ratio of 1-3;
s15, filling a silk fibroin salt solution into a dialysis bag, putting the dialysis bag into distilled water for dialysis for 3-5 days, changing the distilled water every 12 hours, and after the dialysis is finished, transferring a mixture in the dialysis bag into a beaker to obtain a silk fibroin solution;
s16, putting the silk fibroin solution into a water bath thermostat with the temperature of 54-58 ℃ for water bath for 10-20min, adjusting the pH value of the silk fibroin solution to 6.0-7.0 by using an ammonia water solution with the mass fraction of 25%, adding neutral protease according to the mass ratio of the neutral protease to the silk fibroin solution of 1-15, stirring for 1-2h under the condition of the rotation speed of 50-100r/min, cooling to room temperature, and filtering by using an ultrafiltration membrane with the enzyme removing aperture of 0.22 mu m to obtain a nano-scale silk fibroin solution;
and S17, pouring the nano-scale silk fibroin solution into a round-bottom flask, placing the round-bottom flask on a rotary evaporator for concentration, stopping concentration when the volume of the solution is 1/3, placing the nano-scale silk fibroin concentrated solution in an ultra-low temperature refrigerator at minus 70 ℃ for pre-freezing for 12 hours, and then carrying out vacuum drying for 36 hours at minus 110 ℃ to obtain nano-scale silk fibroin powder.
4. The biofilm material according to claim 3, wherein the ratio of the cocoon shell, the ether and the absolute ethanol solution in step S12 is 1g:20-30 mL; in the step S16, the enzyme activity of the neutral protease is 20 ten thousand mu/g.
5. The biofilm material of claim 1, wherein said microcrystalline cellulose and NaIO in step S21 4 The mass ratio of the chitosan to the acetic acid solution with the mass fraction of 3-5% in the step S22 is 1g:10-20mL, wherein the dosage ratio of the oxidized microcrystalline fiber, the deionized water and the EDC and NHS composite coupling agent in the step S23 is 1g:20-30mL:0.1-05g; in step S24, the volume ratio of the oxidized microcrystalline fiber treatment solution to the chitosan dispersion solution is 1:1-3.
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