CN109498847A - A kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane - Google Patents
A kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/042—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/145—Hydrogels or hydrocolloids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
Abstract
The invention discloses a kind of preparation methods of degradable hemostatic bacteriostatic biological medicinal membrane, belong to medical technical field of membrane.The present invention is first with shrimp shell, crab shell is that raw material prepares chitin fiber, again with gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene, tetrahydrofuran etc. is that hydrogel is made in raw material, by chitin fiber and hydrogel hybrid reaction, so that the active group on methylcellulose surface and the active group of hydrogel surface generate Hydrogen Binding Adsorption power and are combined together two kinds of substances, obtain modified hydrogel, modified hydrogel is put into high-voltage electrostatic spinning device, composite nano-fiber membrane is made, again through hot-pressing processing up to antibacterial biological medicinal membrane degradable and with hemostatic function, its degradation time is short, bleeding stopping period greatly shortens, with good haemostatic effect, and to Escherichia coli, staphylococcus aureus, the fungistatic effect of Candida albicans is obviously improved, it has broad application prospects.
Description
Technical field
The invention discloses a kind of preparation methods of degradable hemostatic bacteriostatic biological medicinal membrane, belong to medical membrane technology neck
Domain.
Background technique
It is reported that 90% surgical operation postoperative will lead to different degrees of adhesion.After postoperative tissue adhesion bring
Losing disease is: operative site constant pain, post-operation adhesion lose partial function, and increase the difficulty and generation performed the operation again
The potentiality of complication.In surgical operation, preventing post-operation adhesion product is still that market is badly in need of.
Operation antiblocking film is also known as absorbable medical film, is a kind of ultra-thin comfortable semi-permeable membrane.With good waterproof,
Fungi-proofing, ventilative, low sensitization, it is transparent, high-elastic the features such as, CO can be degraded within the expected time2And H2The small molecules such as O are by human body
It absorbs or excretes.In surgical operation, is acted on using " temporary barrier " of film, is isolated in the surface of a wound between surrounding tissue,
With the generation of prevention of postoperative adhesion.Biological antiadhesion barrier is suitable for many diseases, including common surgical operation, gynemetrics's hand
Art, bone surgery etc..It is necessary to meet following condition for good biological medicinal membrane: (1) there is certain hemostatic function, it can be in bleeding
In the case of use；(2) there is suitable mechanical strength, convenient for operation；(3) self adhesion property is good, if adhesiveness is bad, operation
Adhesion membrane is very restricted in the application, as between peritonaeum and intestinal tube, between intestinal tube and intestinal tube, since intestinal tube is in continuous wriggling
In, biological medicinal membrane is easy sliding, it is possible to the position that health is lossless originally be caused to cause new wound.At present in clinical practice
There are many kinds of the materials for being used to prepare operation antiblocking, as Sodium Hyaluronate, polylactic acid, chitosan, oxidized regenerated cellulose and
Hydroxymethyl cellulose etc., but above-mentioned material limited pliability, are unfavorable for practical application.
Generally existing bleeding or oozing phenomenon in surgical procedure, which greatly limits the use scopes of biological medicinal membrane, together
When increased adhesion probability.Some researches show that gel has local hemostasis effect, inhibits the formation of fibrin beam, has
Conducive to tissue adhesion, but gel poor mechanical property is reduced, it is unfavorable for operating.
The generally existing matter of presently commercially available polylactic acid membrane is crisp uneven, and flexibility is poor, non-stretchable, in technical indicator,
Index of correlation without reflection tensile strength, properties of product are hard, crisp, and using effect is very poor.In addition, existing medical films are to skin at present
Skin there are biggish irritation, there are anti-microbial properties it is poor, poor biocompatibility and wound healing are slow the disadvantages of, handle chronic wound
When, often effect is not ideal enough.
Therefore, a kind of quality is stable, degradability is good, haemostatic effect is good there is an urgent need to researching and developing at present, and has antibacterial function
Can medical films meet the needs of patient.
Summary of the invention
Present invention mainly solves the technical issues of, for presently, there are the antibacterial of biological medicinal membrane, haemostatic effect it is poor, can
The defect of degradability difference provides a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane, it is characterised in that specific preparation step are as follows:
(1) shrimp shell, crab shell are put into grinder, grind 20~30min, obtains abrasive flour, abrasive flour, hydrochloric acid are put into
In reaction kettle, after being stirred to react 1~3h, it is added sodium hydroxide solution into reaction kettle, adjusts pH to 8~9, it is stirred to react 1~
After 3h, hydrochloric acid is added into reaction kettle, adjusting pH is neutrality, obtains mixed liquor；
(2) it pours into after mixing above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite in stirring instrument, is put into after stirring 20~30min
In baking oven, setting oven temperature is 60~70 DEG C, and dry 1~2h is to get chitin；
(3) above-mentioned chitin, lithium chloride, dimethylacetamide solution are poured into stirring instrument, stirs 20~30min, is glued
Isopropanol is added into thick liquid for thick liquid, stirs evenly, and obtains coagulated fibre, and coagulated fibre is done with distilled water flushing
It is put into baking oven after net, under conditions of temperature is 60~70 DEG C, dry 1~2h is spare to get chitin fiber；
(4) it is put into after mixing gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene in stirring instrument, is stirred to react 20~30min,
Mixture is obtained, then sodium bicarbonate is added into mixture, obtains pretreatment object；
(5) it after mixing above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile, is put into have and stir
It mixes in the reaction kettle of device, is stirred to react 1~2h, obtain hydrogel；
(6) it after mixing spare chitin fiber and hydrogel obtained above, is put into the reaction kettle with blender, adds
Heat is warming up to 40~50 DEG C, is stirred to react 20~30min, and modified hydrogel is made；
(7) above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device, starts HV generator, will changes
Property hydrogel with infusion pump squeeze out sprayed again by spinning nozzle, the mixed liquor jet stream of ejection, which is cured, to form composite nano-fiber membrane,
It is arranged on collecting board with unordered shape, is cured after hot press suppresses 30~40min up to a kind of degradable hemostatic bacteriostatic biology
With the preparation method of film.
Abrasive flour described in step (1), hydrochloric acid mass ratio be 1 ︰ 2, the mass fraction of hydrochloric acid is 5%, sodium hydroxide
The mass fraction of solution is 5%, and the mass fraction of hydrochloric acid is 5%.
Above-mentioned mixed liquor described in step (2), potassium permanganate, sodium hydrogensulfite mass ratio be 3 ︰, 1 ︰ 1.
Above-mentioned chitin described in step (3), lithium chloride, dimethylacetamide solution mass ratio be 12 ︰, 1 ︰ 20, diformazan
The mass fraction of yl acetamide solution is 30%, and the quality of isopropanol is the 6~9% of thick liquid quality.
Gamma-polyglutamic acid described in step (4), bromination of n-butane, allyl bromide, bromoallylene mass ratio be 2 ︰, 1 ︰ 1, sodium bicarbonate
Quality be mixture quality 20~30%.
The matter of above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile described in step (5)
Amount score is 3 ︰, 3 ︰, 2 ︰ 1.
The mass ratio of spare chitin fiber and hydrogel obtained above described in step (6) is 1 ︰ 1.
Pressure in hot press described in step (7) is 2~3MPa.
The beneficial effects of the present invention are:
(1) present invention prepares chitin fiber using shrimp shell, crab shell as raw material first, then with gamma-polyglutamic acid, bromination of n-butane,
Allyl bromide, bromoallylene is raw material, and the mixture containing halogenated hydrocarbon is made in hybrid reaction, by the mixture containing halogenated hydrocarbon, tetrahydrofuran,
Hydroxyethyl methacrylate, azodiisobutyronitrile hybrid reaction obtain hydrogel, after chitin fiber and hydrogel are mixed
It is reacted under heating condition, so that the active group on methylcellulose surface and the active group of hydrogel surface generate Hydrogen Binding Adsorption
Power and two kinds of substances are combined together, obtain modified hydrogel, modified hydrogel be put into high-voltage electrostatic spinning device
Composite nano-fiber membrane is made, then through hot-pressing processing up to degradable hemostatic bacteriostatic biological medicinal membrane, the present invention is first with shrimp
Shell, crab shell are that raw material prepares chitin fiber, and chitin fiber has antibacterial, anti-inflammatory, hemostasis, analgesia, promotes tissue growth, promotees
Into the effect of wound healing, chitin is widely present in the cell of rudimentary plant mushroom, algae, arthropod shrimp, crab, fly maggot and
The shell of insect, shellfish, molluscan shell and cartilage, in the cell wall of higher mammal, therefore its is from a wealth of sources, is easy to obtain
It takes, it is nontoxic to the human body non-stimulated, can be decomposed and absorb by the intracorporal lysozyme of people, have good bio-compatible with tissue
Property, it is biodegradable, there is antibacterial, haemostatic effect, so that medical films produced by the present invention have antibacterial bacteriostatic, haemostatic effect；
(2) for the present invention again using gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene as raw material, hybrid reaction, which is made, contains halogenated hydrocarbon
Mixture, polyglutamic acid is nontoxic to human body and environment, biodegradable, have bacteriostasis, be easily cross-linked to form hydrogel, halogen
Sodium halide can be generated under alkaline condition by changing hydrocarbon, while the hydrogen ion in the carboxyl on gamma-polyglutamic acid side chain will be with carbonic acid
Hydrogen radical generates water and carbon dioxide, so that the group of institute's band in halides is connected in a manner of ester bond with gamma-polyglutamic acid,
The use of bromination of n-butane improves the hydrophobicity of gamma-polyglutamic acid, is conducive to the preparation of hydrogel, allyl bromide, bromoallylene is in addition to improving
Outside γ-polyglutamic hydrophobicity, double-strand therein is conducive to be esterified gamma-polyglutamic acid formation reticular structure, increases hydrogel
Water holding capacity adds hydroxyethyl methacrylate as crosslinking agent using tetrahydrofuran as the solvent of ester dissolubility crosslinking agent, with
And azodiisobutyronitrile, as initiator, oil bath is stirred so that the gamma-polyglutamic acid after esterification spontaneously forms hydrogel, hydrogel
With local hemostasis effect, inhibits the formation of fibrin beam, advantageously reduce tissue adhesion, it is molten using tetrahydrofuran as ester
Property crosslinking agent solvent, add hydroxyethyl methacrylate as crosslinking agent and azodiisobutyronitrile as initiator, oil
So that the gamma-polyglutamic acid after esterification spontaneously forms hydrogel, hydrogel has local hemostasis effect for bath stirring, inhibits fibrin
The formation of albumen beam advantageously reduces tissue adhesion, reacts, makes in a heated condition after chitin fiber and hydrogel are mixed
The active group of the active group and hydrogel surface that obtain methylcellulose surface generates Hydrogen Binding Adsorption power and makes two kinds of substances
It is combined together, obtains modified hydrogel, modified hydrogel is biodegradable, and antibacterial, haemostatic effect is promoted, by modified hydrogel
It is put into high-voltage electrostatic spinning device and composite nano-fiber membrane is made, then through hot-pressing processing up to degradable hemostatic bacteriostatic biology
Medical films, the present invention have broad application prospects.
Specific embodiment
Shrimp shell, crab shell are put into grinder, 20~30min is ground, obtains abrasive flour, by abrasive flour, quality point
Number is that 1 ︰ 2 is put into reaction kettle for 5% hydrochloric acid in mass ratio, and after being stirred to react 1~3h, mass fraction is added into reaction kettle
For 5% sodium hydroxide solution, pH to 8~9 is adjusted, after being stirred to react 1~3h, it is 5% that mass fraction is added into reaction kettle
Hydrochloric acid, adjust pH be neutrality, obtain mixed liquor；It is in mass ratio 3 ︰, 1 ︰ by above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite
It pouring into after 1 mixing in stirring instrument, is put into baking oven after stirring 20~30min, setting oven temperature is 60~70 DEG C, dry 1
~2h is to get chitin；It is in mass ratio by the dimethylacetamide solution that above-mentioned chitin, lithium chloride, mass fraction are 30%
12 ︰, 1 ︰ 20 is poured into stirring instrument, is stirred 20~30min, is obtained thick liquid, and thick liquid quality 6 is added into thick liquid
~9% isopropanol, stirs evenly, and obtains coagulated fibre, by coagulated fibre with distilled water flushing it is clean after be put into baking oven,
Under conditions of temperature is 60~70 DEG C, dry 1~2h is spare to get chitin fiber；By gamma-polyglutamic acid, the positive fourth of bromo
Alkane, allyl bromide, bromoallylene are to be put into stirring instrument after 2 ︰, 1 ︰ 1 is mixed in mass ratio, are stirred to react 20~30min, obtain mixture, then
The sodium bicarbonate of mixture quality 20~30% is added into mixture, obtains pretreatment object；By above-mentioned pretreatment object, tetrahydro furan
Mutter, hydroxyethyl methacrylate, azodiisobutyronitrile by mass fraction be 3 ︰, 3 ︰, 2 ︰ 1 mixing after, be put into the anti-of blender
It answers in kettle, is stirred to react 1~2h, obtain hydrogel；In mass ratio by spare chitin fiber and hydrogel obtained above
It after 1 ︰ 1 mixing, is put into the reaction kettle with blender, is heated to 40~50 DEG C, be stirred to react 20~30min, make
Hydrogel must be modified；Above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device, high-pressure electrostatic is started
Modified hydrogel is squeezed out with infusion pump and is sprayed again by spinning nozzle by device, and the mixed liquor jet stream of ejection is cured to form composite Nano
Tunica fibrosa is arranged on collecting board with unordered shape, can be dropped to obtain the final product after hot press suppresses 30~40min with the pressure of 2~3MPa
Solution type hemostatic bacteriostatic biological medicinal membrane.
Example 1
Shrimp shell, crab shell are put into grinder, 20min is ground, obtains abrasive flour, is 5% by abrasive flour, mass fraction
Hydrochloric acid is that 1 ︰ 2 is put into reaction kettle in mass ratio, and after being stirred to react 1h, the hydrogen-oxygen that mass fraction is 5% is added into reaction kettle
Change sodium solution, adjust pH to 8, after being stirred to react 1h, the hydrochloric acid that mass fraction is 5% is added into reaction kettle, adjusts during pH is
Property, obtain mixed liquor；It is in mass ratio to pour into stirring instrument after 3 ︰, 1 ︰ 1 is mixed by above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite
In, it is put into baking oven after stirring 20min, setting oven temperature is 60 DEG C, and dry 1h is to get chitin；By above-mentioned chitin,
The dimethylacetamide solution that lithium chloride, mass fraction are 30% is that 12 ︰, 1 ︰ 20 is poured into stirring instrument in mass ratio, stirring
20min obtains thick liquid, and the isopropanol of thick liquid quality 6% is added into thick liquid, stirs evenly, and it is fine to obtain solidification
Dimension, by coagulated fibre with distilled water flushing it is clean after be put into baking oven, under conditions of temperature is 60 DEG C, dry 1h is to get first
Shell cellulose fiber, it is spare；It is in mass ratio to be put into stirring after 2 ︰, 1 ︰ 1 is mixed by gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene
In instrument, it is stirred to react 20min, obtains mixture, then the sodium bicarbonate of mixture quality 20% is added into mixture, is obtained pre-
Processed material；It is 3 ︰, 3 ︰ that above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile, which are pressed mass fraction,
After 2 ︰ 1 mixing, it is put into the reaction kettle with blender, is stirred to react 1h, obtain hydrogel；By spare chitin fiber and
Hydrogel obtained above is after 1 ︰ 1 is mixed, to be put into the reaction kettle with blender, be heated to 40 DEG C in mass ratio,
It is stirred to react 20min, modified hydrogel is made；Above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device,
Start HV generator, modified hydrogel is squeezed out with infusion pump and is sprayed again by spinning nozzle, the mixed liquor jet stream quilt of ejection
It is formed by curing composite nano-fiber membrane, is arranged on collecting board with unordered shape, after hot press suppresses 30min with the pressure of 2MPa
Up to degradable hemostatic bacteriostatic biological medicinal membrane.
Example 2
Shrimp shell, crab shell are put into grinder, 25min is ground, obtains abrasive flour, is 5% by abrasive flour, mass fraction
Hydrochloric acid is that 1 ︰ 2 is put into reaction kettle in mass ratio, and after being stirred to react 2h, the hydrogen-oxygen that mass fraction is 5% is added into reaction kettle
Change sodium solution, adjust pH to 8, after being stirred to react 2h, the hydrochloric acid that mass fraction is 5% is added into reaction kettle, adjusts during pH is
Property, obtain mixed liquor；It is in mass ratio to pour into stirring instrument after 3 ︰, 1 ︰ 1 is mixed by above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite
In, it is put into baking oven after stirring 25min, setting oven temperature is 65 DEG C, and dry 1h is to get chitin；By above-mentioned chitin,
The dimethylacetamide solution that lithium chloride, mass fraction are 30% is that 12 ︰, 1 ︰ 20 is poured into stirring instrument in mass ratio, stirring
25min obtains thick liquid, and the isopropanol of thick liquid quality 8% is added into thick liquid, stirs evenly, and it is fine to obtain solidification
Dimension, by coagulated fibre with distilled water flushing it is clean after be put into baking oven, under conditions of temperature is 65 DEG C, dry 1h is to get first
Shell cellulose fiber, it is spare；It is in mass ratio to be put into stirring after 2 ︰, 1 ︰ 1 is mixed by gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene
In instrument, it is stirred to react 25min, obtains mixture, then the sodium bicarbonate of mixture quality 25% is added into mixture, is obtained pre-
Processed material；It is 3 ︰, 3 ︰ that above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile, which are pressed mass fraction,
After 2 ︰ 1 mixing, it is put into the reaction kettle with blender, is stirred to react 1h, obtain hydrogel；By spare chitin fiber and
Hydrogel obtained above is after 1 ︰ 1 is mixed, to be put into the reaction kettle with blender, be heated to 45 DEG C in mass ratio,
It is stirred to react 25min, modified hydrogel is made；Above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device,
Start HV generator, modified hydrogel is squeezed out with infusion pump and is sprayed again by spinning nozzle, the mixed liquor jet stream quilt of ejection
It is formed by curing composite nano-fiber membrane, is arranged on collecting board with unordered shape, after hot press suppresses 35min with the pressure of 2MPa
Up to degradable hemostatic bacteriostatic biological medicinal membrane.
Example 3
Shrimp shell, crab shell are put into grinder, 30min is ground, obtains abrasive flour, is 5% by abrasive flour, mass fraction
Hydrochloric acid is that 1 ︰ 2 is put into reaction kettle in mass ratio, and after being stirred to react 3h, the hydrogen-oxygen that mass fraction is 5% is added into reaction kettle
Change sodium solution, adjust pH to 9, after being stirred to react 3h, the hydrochloric acid that mass fraction is 5% is added into reaction kettle, adjusts during pH is
Property, obtain mixed liquor；It is in mass ratio to pour into stirring instrument after 3 ︰, 1 ︰ 1 is mixed by above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite
In, it is put into baking oven after stirring 30min, setting oven temperature is 70 DEG C, and dry 2h is to get chitin；By above-mentioned chitin,
The dimethylacetamide solution that lithium chloride, mass fraction are 30% is that 12 ︰, 1 ︰ 20 is poured into stirring instrument in mass ratio, stirring
30min obtains thick liquid, and the isopropanol of thick liquid quality 9% is added into thick liquid, stirs evenly, and it is fine to obtain solidification
Dimension, by coagulated fibre with distilled water flushing it is clean after be put into baking oven, under conditions of temperature is 70 DEG C, dry 2h is to get first
Shell cellulose fiber, it is spare；It is in mass ratio to be put into stirring after 2 ︰, 1 ︰ 1 is mixed by gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene
In instrument, it is stirred to react 30min, obtains mixture, then the sodium bicarbonate of mixture quality 30% is added into mixture, is obtained pre-
Processed material；It is 3 ︰, 3 ︰ that above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile, which are pressed mass fraction,
After 2 ︰ 1 mixing, it is put into the reaction kettle with blender, is stirred to react 2h, obtain hydrogel；By spare chitin fiber and
Hydrogel obtained above is after 1 ︰ 1 is mixed, to be put into the reaction kettle with blender, be heated to 50 DEG C in mass ratio,
It is stirred to react 30min, modified hydrogel is made；Above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device,
Start HV generator, modified hydrogel is squeezed out with infusion pump and is sprayed again by spinning nozzle, the mixed liquor jet stream quilt of ejection
It is formed by curing composite nano-fiber membrane, is arranged on collecting board with unordered shape, after hot press suppresses 40min with the pressure of 3MPa
Up to degradable hemostatic bacteriostatic biological medicinal membrane.
Comparative example
By taking the biological medicinal membrane of Guangzhou company production as an example
Biological medicinal membrane in degradable hemostatic bacteriostatic biological medicinal membrane produced by the present invention and comparative example is detected, is examined
The results are shown in Table 1 for survey:
Degradation time test
With 3% pentobarbital solution intraperitoneal injection of anesthesia rat, rat is lain on the back and is fixed on operating table, abdomen is successively opened, dissociated simultaneously
Exposure liver lobus sinister, cuts one piece of hepatic tissue (5mm × 3mm × 2mm) in liver lobus sinister middle position with tissue forceps, causes to open wide
Type wound is pasted on degradable hemostatic bacteriostatic biological medicinal membrane made from Examples 1 to 3 and right after free bleeding 5s respectively
On the medical films of ratio, abdominal cavity is closed in suture after handling the surface of a wound, takes 6 in every group from every group weekly in the postoperative 3rd, 4,5,6
Rat anesthesia is cut open the belly, and the degradation situation of the degradable hemostatic bacteriostatic biological medicinal membrane of example 1~3 is observed.
Bleeding stopping period test
New zealand white rabbit 15 are selected, the preparation liver middle period cuts off Hemorrhage Model, and is made in bleeding part using example 1~3
Degradable hemostatic bacteriostatic biological medicinal membrane and comparative example medical films compressing wound and start timing, no blood exudation is
Stop blooding successfully.
Bacteriostasis rate test
Escherichia coli bacteriostasis rate, which is tested, carries out bacteriostasis property detection by the regulation of JC/T897-2002.
Staphylococcus aureus bacteriostasis rate, which is tested, carries out bacteriostasis property detection by the regulation of JC/T897-2002.
The test of Candida albicans bacteriostasis rate carries out performance detection by the regulation of GB/T20944.2-2007.
1 performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Degradation time (d) | 28 | 26 | 24 | 40 |
| Bleeding stopping period (s) | 46 | 41 | 39 | 98 |
| Escherichia coli bacteriostasis rate (%) | 99.62 | 99.72 | 99.97 | 87.36 |
| Staphylococcus aureus bacteriostasis rate (%) | 99.35 | 99.42 | 99.56 | 86.85 |
| Candida albicans bacteriostasis rate (%) | 99.45 | 99.72 | 99.85 | 84.78 |
According to 1 data of table it is found that degradable hemostatic bacteriostatic biological medicinal membrane produced by the present invention, has degradation time short, only
The blood time is short, while having good haemostatic effect, and the suppression to Escherichia coli, staphylococcus aureus, Candida albicans
Bacterium effect is obviously improved, and is had better performance compared to common biological medicinal membrane, is had broad application prospects.
Claims (8)
1. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane, it is characterised in that specific preparation step are as follows:
(1) shrimp shell, crab shell are put into grinder, grind 20~30min, obtains abrasive flour, abrasive flour, hydrochloric acid are put into
In reaction kettle, after being stirred to react 1~3h, it is added sodium hydroxide solution into reaction kettle, adjusts pH to 8~9, it is stirred to react 1~
After 3h, hydrochloric acid is added into reaction kettle, adjusting pH is neutrality, obtains mixed liquor；
(2) it pours into after mixing above-mentioned mixed liquor, potassium permanganate, sodium hydrogensulfite in stirring instrument, is put into after stirring 20~30min
In baking oven, setting oven temperature is 60~70 DEG C, and dry 1~2h is to get chitin；
(3) above-mentioned chitin, lithium chloride, dimethylacetamide solution are poured into stirring instrument, stirs 20~30min, is glued
Isopropanol is added into thick liquid for thick liquid, stirs evenly, and obtains coagulated fibre, and coagulated fibre is done with distilled water flushing
It is put into baking oven after net, under conditions of temperature is 60~70 DEG C, dry 1~2h is spare to get chitin fiber；
(4) it is put into after mixing gamma-polyglutamic acid, bromination of n-butane, allyl bromide, bromoallylene in stirring instrument, is stirred to react 20~30min,
Mixture is obtained, then sodium bicarbonate is added into mixture, obtains pretreatment object；
(5) it after mixing above-mentioned pretreatment object, tetrahydrofuran, hydroxyethyl methacrylate, azodiisobutyronitrile, is put into have and stir
It mixes in the reaction kettle of device, is stirred to react 1~2h, obtain hydrogel；
(6) it after mixing spare chitin fiber and hydrogel obtained above, is put into the reaction kettle with blender, adds
Heat is warming up to 40~50 DEG C, is stirred to react 20~30min, and modified hydrogel is made；
(7) above-mentioned modified hydrogel is put into the hopper of high-voltage electrostatic spinning device, starts HV generator, will changes
Property hydrogel with infusion pump squeeze out sprayed again by spinning nozzle, the mixed liquor jet stream of ejection, which is cured, to form composite nano-fiber membrane,
It is arranged on collecting board with unordered shape, up to degradable hemostatic bacteriostatic biological medicinal membrane after hot press suppresses 30~40min.
2. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Abrasive flour described in step (1), hydrochloric acid mass ratio be 1 ︰ 2, the mass fraction of hydrochloric acid is 5%, the matter of sodium hydroxide solution
Measuring score is 5%, and the mass fraction of hydrochloric acid is 5%.
3. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Above-mentioned mixed liquor described in step (2), potassium permanganate, sodium hydrogensulfite mass ratio be 3 ︰, 1 ︰ 1.
4. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Above-mentioned chitin described in step (3), lithium chloride, dimethylacetamide solution mass ratio be 12 ︰, 1 ︰ 20, dimethyl acetamide
The mass fraction of solution is 30%, and the quality of isopropanol is the 6~9% of thick liquid quality.
5. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Gamma-polyglutamic acid described in step (4), bromination of n-butane, allyl bromide, bromoallylene mass ratio be 2 ︰, 1 ︰ 1, the quality of sodium bicarbonate is
The 20~30% of mixture quality.
6. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Above-mentioned pretreatment object, tetrahydrofuran described in step (5), hydroxyethyl methacrylate, azodiisobutyronitrile mass fraction be
3 ︰, 3 ︰, 2 ︰ 1.
7. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
The mass ratio of spare chitin fiber and hydrogel obtained above described in step (6) is 1 ︰ 1.
8. a kind of preparation method of degradable hemostatic bacteriostatic biological medicinal membrane according to claim 1, it is characterised in that:
Pressure in hot press described in step (7) is 2~3MPa.
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| CN113736147A (en) * | 2021-09-14 | 2021-12-03 | 南京大学 | Waterproof and antibacterial chitosan transparent film and preparation method thereof |
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