CN113082299B - Degradable porous PVA/starch biological membrane and preparation method thereof - Google Patents
Degradable porous PVA/starch biological membrane and preparation method thereof Download PDFInfo
- Publication number
- CN113082299B CN113082299B CN202110292801.XA CN202110292801A CN113082299B CN 113082299 B CN113082299 B CN 113082299B CN 202110292801 A CN202110292801 A CN 202110292801A CN 113082299 B CN113082299 B CN 113082299B
- Authority
- CN
- China
- Prior art keywords
- starch
- pva
- biological membrane
- parts
- chitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 229920002472 Starch Polymers 0.000 title claims abstract description 61
- 235000019698 starch Nutrition 0.000 title claims abstract description 61
- 239000008107 starch Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920001661 Chitosan Polymers 0.000 claims abstract description 43
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229960003638 dopamine Drugs 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 36
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 21
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 239000003102 growth factor Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 230000008467 tissue growth Effects 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 239000005313 bioactive glass Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 claims description 2
- 229950005308 oxymethurea Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- BLSAPDZWVFWUTL-UHFFFAOYSA-N 2,5-dioxopyrrolidine-3-sulfonic acid Chemical compound OS(=O)(=O)C1CC(=O)NC1=O BLSAPDZWVFWUTL-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 210000001519 tissue Anatomy 0.000 description 6
- 102000007350 Bone Morphogenetic Proteins Human genes 0.000 description 4
- 108010007726 Bone Morphogenetic Proteins Proteins 0.000 description 4
- 229940112869 bone morphogenetic protein Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 210000002569 neuron Anatomy 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000017423 tissue regeneration Effects 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- WJQDJDVDXAAXSB-UHFFFAOYSA-N 5-sulfanylidenepyrrolidin-2-one Chemical compound O=C1CCC(=S)N1 WJQDJDVDXAAXSB-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000922 anti-bactericidal effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- A61L31/02—Inorganic materials
- A61L31/026—Ceramic or ceramic-like structures, e.g. glasses
-
- 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
- A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- A61L31/141—Plasticizers
-
- 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
- A61L31/146—Porous materials, e.g. foams or sponges
-
- 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
-
- 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
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
- A61L2300/414—Growth factors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Heart & Thoracic Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a degradable porous PVA/starch biological membrane and a preparation method thereof, wherein the existing PVA membrane formula is optimized, and the optimized formula comprises the following components in parts by weight: 100 parts of PVA, 10-50 parts of starch, 5-20 parts of chitosan, 5-20 parts of ceramic powder, 0.2-2 parts of dopamine, 0.1-1 part of plasticizer and 0.1-1 part of cross-linking agent. The film forming sequence of the raw materials in the preparation process is limited, particularly the film forming sequence of the chitosan layer and the ceramic powder layer, the characteristics of the formula can be better adapted, the effects of various components are exerted to the maximum extent, the mechanical property and the biocompatibility of a target biological film can be effectively improved, and the mechanical property and the degradation speed of the film can be controlled by adjusting the weight part ratio of PVA to starch, so that the application requirements in different clinical practices can be met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a degradable porous PVA/starch biological membrane and a preparation method thereof.
Background
The Guided Tissue Regeneration (GTR) technology is a new technology developed in the early 90 s at the end of the 80 s. The GTR membrane has the function of creating a space beneficial to tissue healing and plays a role in self reconstruction of tissues to a greater extent, and the principle is that a damaged area is isolated from surrounding tissues by utilizing the physical barrier function of the membrane to create a relatively closed tissue environment, so that the regeneration function of specific tissues is played to the greatest extent.
The existing GTR membrane such as a general polytetrafluoroethylene GTR membrane has good mechanical strength, but has the problems of incapability of self degradation, secondary operation removal, poor cell affinity, easy wound cracking, early membrane exposure and great pain brought to patients by the secondary operation which is necessary for influencing wound healing, and in addition, the inherent biological inertia of the membrane causes that the membrane cannot be used for guiding tissue regeneration of a large defect. Therefore, an ideal membrane material should be one that can degrade and absorb itself during or after proper tissue healing and the product is harmless to the body.
PVA is a commonly used film material, and is characterized by no toxicity, no irritation, good film forming property, difficult destruction by microorganism, no mould growth, best flexibility, hygroscopicity and water solubility, and no irritation and no influence on the biological activity of medicinal components when being used as a carrier; but has the problems of no anti-inflammatory and bactericidal performance, poor mechanical performance, difficult control of degradation speed, improvement of biocompatibility and the like.
Disclosure of Invention
The invention provides a degradable porous PVA/starch biological membrane and a preparation method thereof, aims at solving the problems of poor mechanical property, poor controllability of degradation speed, insufficient biological activity and the like of the existing PVA membrane, optimizes the formula, and provides the degradable porous PVA/starch biological membrane with more excellent performance by matching with a corresponding process preparation method.
The technical scheme adopted by the invention is as follows:
a degradable porous PVA/starch biological membrane comprises the following components in parts by weight:
100 parts of PVA;
10-50 parts of starch;
5-20 parts of chitosan;
5-20 parts of ceramic powder;
0.2-2 parts of dopamine;
0.1-1 part of a plasticizer;
0.1-1 part of a crosslinking agent.
Preferably, the chitosan has an average relative molecular mass of not less than 5 × 105The high molecular weight chitosan and the average relative molecular mass are not more than 1 x 104A mixture of low molecular weight chitosans of (a).
Preferably, the ceramic powder is any one of hydroxyapatite, bioactive glass, calcium phosphate, alumina or zirconia.
Preferably, the plasticizer is at least one of glycerol, diglycerol, ethylene glycol, polyethylene glycol and propylene glycol.
Preferably, the crosslinking agent is any one of carbodiimide, thiosuccinimide, glutaraldehyde, dimethylol urea, and trimethylol melamine.
The formula is further optimized, and the components of the degradable porous PVA/starch biological membrane also comprise 0.1-1 part of auxiliary active ingredients.
Preferably, the auxiliary active ingredient is at least one of inorganic antibacterial agent, tissue growth factor and slow-release medicine.
The invention also provides a preparation method of the degradable porous PVA/starch biological membrane, which comprises the following steps:
s1: adding the PVA, the starch and the plasticizer into water, stirring and dispersing, preparing a film forming solution with the mass fraction of 25-45% at 50-80 ℃, and then freezing and vacuumizing for reaction for 12-72 hours to obtain a first biological film;
s2: preparing the chitosan into a chitosan solution with the mass concentration not less than 3%, soaking the first biological membrane in the chitosan solution for 0.2-1 hour, and then cleaning with water to obtain a second biological membrane;
s3: dissolving the dopamine in a buffer solution, adding the ceramic powder, then oscillating and dispersing, reacting for 12-72 hours under stirring, and centrifuging to remove large particles to obtain an auxiliary solution;
s4: soaking the second biological membrane in the auxiliary solution for 0.2-1 hour, and then washing with water to obtain a third biological membrane;
s5: preparing the cross-linking agent into a cross-linking solution with the mass concentration not less than 1%, soaking the third biological membrane in the cross-linking solution for 5-10 hours, washing with water, and drying to obtain the degradable porous PVA/starch biological membrane.
Preferably, the buffer used in the step S3 has a pH of 8 to 9.
Further optimization, the preparation method of the degradable porous PVA/starch biological membrane further comprises the following steps:
and soaking the prepared degradable porous PVA/starch biological membrane in a solution containing the auxiliary active ingredient for 5-10 hours to obtain the degradable porous PVA/starch biological membrane loaded with the auxiliary active ingredient.
The beneficial effects of the invention are:
the invention optimizes the formula of the degradable porous PVA/starch biological membrane, takes water-soluble high-molecular PVA and biodegradable material starch as basic raw materials, and introduces materials such as chitosan, ceramic powder, dopamine and the like, thereby effectively improving the mechanical property and biocompatibility of the target biological membrane.
The polyvinyl alcohol has excellent film forming property and degradability, and can further improve the degradability of the material by matching with starch, the degradation product has no pollution to the environment, the cost of the biological film is reduced, and the economic benefit is increased. Further optimizing, the invention can control the mechanical property and the degradation speed of the film by adjusting the weight part ratio of PVA to starch. After the introduction of the chitosan layer, the hydrophilicity of the film was slightly decreased, but the tensile strength and elongation at break were both increased. And the formation of ceramic powder with bioactivity, such as hydroxyapatite, bioactive glass, calcium phosphate, alumina or zirconia and other film layers, can obviously improve the biocompatibility of the target biological film. In addition, after ceramic powder such as hydroxyapatite and other bioactive components are introduced into the target biological membrane, the Young modulus of the surface of the biological membrane can be greatly increased.
In the invention, ceramic powder such as hydroxyapatite is dissolved in dopamine solution during preparation, and the surface of the hydroxyapatite is modified by utilizing dopamine autopolymerization technology so as to improve the dispersibility of the hydroxyapatite. After modification, the apparent particle size of the hydroxyapatite is reduced, and the dispersibility of the hydroxyapatite in water is greatly increased. Furthermore, the addition of the cross-linking agents and the auxiliary agents can carry out chemical cross-linking on the product film of the initial prototype, so that the stability of the target product can be further improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. 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 degradable porous PVA/starch biological film is characterized in that:
the paint comprises the following components in parts by weight:
100 parts of PVA;
50 parts of starch;
10 parts of chitosan;
20 parts of ceramic powder;
2 parts of dopamine;
0.5 part of a plasticizer;
0.5 part of a crosslinking agent.
Wherein,
the polymerization degree of the PVA is 2000, and the alcoholysis degree is 85%.
The chitosan has an average relative molecular mass of 6 × 105In another embodiment, the molar ratio of the high molecular weight chitosan to the low molecular weight chitosan is 1: 1.
In this embodiment, the ceramic powder is hydroxyapatite, the plasticizer is glycerol, and the cross-linking agent is glutaraldehyde.
The preparation method of the degradable porous PVA/starch biological membrane specifically comprises the following steps:
s1: adding the PVA, the starch and the plasticizer into water, stirring and dispersing, preparing a film forming solution with the mass fraction of 30% at 80 ℃, and then freezing and vacuumizing for reaction for 24 hours to obtain a first biological film;
s2: preparing the chitosan into a chitosan solution with the mass concentration of 5%, soaking the first biological membrane in the chitosan solution for 0.5 hour, and then washing with water to obtain a second biological membrane;
s3: dissolving the dopamine in a buffer solution, adding the ceramic powder, then shaking for dispersion, reacting for 24 hours under stirring, and centrifuging to remove large particles to obtain an auxiliary solution;
s4: soaking the second biological membrane in the auxiliary solution for 0.5 hour, and then washing with water to obtain a third biological membrane;
s5: and preparing the cross-linking agent into a cross-linking solution with the mass concentration of 1.5%, soaking the third biological membrane in the cross-linking solution for 5 hours, washing with water, and drying to obtain the degraded porous PVA/starch biological membrane.
Wherein, the buffer solution used in the step S3 can be Tris-HCl buffer solution with the pH value of 8-9.
Example 2:
according to the specific clinical application requirement, on the basis of the embodiment 1, auxiliary active ingredients such as at least one of inorganic antibacterial agents, tissue growth factors and slow-release drugs can be added into the components of the degradable porous PVA/starch biological membrane.
Specifically, in this embodiment:
a degradable porous PVA/starch biological film is characterized in that:
the paint comprises the following components in parts by weight:
100 parts of PVA;
50 parts of starch;
10 parts of chitosan;
20 parts of ceramic powder;
2 parts of dopamine;
0.5 part of a plasticizer;
0.5 part of a crosslinking agent.
0.1 part of auxiliary active ingredients.
Wherein the auxiliary active component is a Bone Morphogenetic Protein (BMP) of a tissue growth factor.
The preparation method of the degradable porous PVA/starch biological membrane specifically comprises the following steps:
s1: adding the PVA, the starch and the plasticizer into water, stirring and dispersing, preparing a film forming solution with the mass fraction of 30% at 80 ℃, and then freezing and vacuumizing for reaction for 24 hours to obtain a first biological film;
s2: preparing the chitosan into a chitosan solution with the mass concentration of 5%, soaking the first biological membrane in the chitosan solution for 0.5 hour, and then washing with water to obtain a second biological membrane;
s3: dissolving the dopamine in a buffer solution, adding the ceramic powder, then oscillating and dispersing, reacting for 24 hours under stirring, and centrifuging to remove large particles to obtain an auxiliary solution;
s4: soaking the second biological membrane in the auxiliary solution for 0.5 hour, and then washing with water to obtain a third biological membrane;
s5: and preparing the cross-linking agent into a cross-linking solution with the mass concentration of 1.5%, soaking the third biological membrane in the cross-linking solution for 5 hours, washing with water, and drying to obtain the degraded porous PVA/starch biological membrane.
S6: and soaking the prepared degradable porous PVA/starch biological membrane in the BMP solution for 5-10 hours to obtain the degradable porous PVA/starch biological membrane loaded with the BMP.
The other conditions were the same as in example 1.
Example 3:
a degradable porous PVA/starch biological membrane is characterized in that:
the paint comprises the following components in parts by weight:
100 parts of PVA;
30 parts of starch;
5 parts of chitosan;
5 parts of ceramic powder;
1 part of dopamine;
0.2 part of plasticizer;
0.2 part of a crosslinking agent.
Wherein the polymerization degree of the polyvinyl alcohol is 2000, and the alcoholysis degree is 85%; the chitosan is a single component and has an average relative molecular mass of 6 x 105The high molecular weight chitosan of (2).
The other conditions were the same as in example 1.
Example 4:
the chitosan used in this example was a single component, low molecular weight chitosan with an average relative molecular mass of 5000.
The other conditions were the same as in example 1.
Comparative example 1:
in this comparative example, no dopamine was added during the preparation of the degraded porous PVA/starch biofilm, and the other conditions were the same as in example 1.
Comparative example 2:
in this comparative example, no hydroxyapatite was added during the preparation of the degradable porous PVA/starch biofilm, and the other conditions were the same as in example 1.
Comparative example 3:
in this comparative example, no chitosan was added during the preparation of the degraded porous PVA/starch biofilm, and the other conditions were the same as in example 1.
First, as the starch content increases, the water solubility shows a tendency to decrease, but the material as a whole still shows good degradability. By utilizing the characteristic, the degradation speed can be controlled by adjusting the weight ratio of PVA to starch, and compared with the degradation speed of the porous PVA/starch biological membrane prepared in the embodiments 1-2 and 3-4, the degradation speed of the porous PVA/starch biological membrane is higher.
In addition, the degraded porous PVA/starch biological films prepared by the chitosan with single component used in the examples 3 and 4 can also play a role in enhancing the mechanical property and biocompatibility of the films. And chitosan with mixed components is preferably used, as shown in examples 1 and 2, so that the film forming of the product is facilitated, and meanwhile, the antibacterial performance of the product can be improved. Wherein, high molecular weight chitosan is easy to form a film, while low molecular weight chitosan has strong penetrability, and the amino groups on the chitosan molecule can play a role in sterilization by accepting cations formed by protons.
After the chitosan layer is soaked, a hydroxyapatite layer with bioactivity is further formed, so that the biocompatibility of a target biological membrane can be obviously improved, and the Young modulus of the surface of the biological membrane can be greatly increased, and the result is shown in table 1:
TABLE 1 Young's modulus test results of the surfaces of the products of examples 1-4 and comparative examples 1-3
| Item | Young's modulus (MPa) |
| Example 1 | 53.5 |
| Example 2 | 52.0 |
| Example 3 | 31.5 |
| Example 4 | 33.0 |
| Comparative example 1 | 4.5 |
| Comparative example 2 | 5.0 |
| Comparative example 3 | 42.5 |
The increase in Young's modulus is of great significance here. Generally, different cell-adapted materials have different degrees of softness, for example, nerve cells are suitable for propagation and differentiation on softer materials, while osteocytes prefer harder materials, and a suitable surface modulus facilitates cell spreading, proliferation and differentiation. Therefore, the present invention provides a method for adjusting the hardness and softness of a target product by adjusting important parts of ceramic powder such as hydroxyapatite for a specific clinical situation. The products obtained in examples 1 to 2 have a high surface modulus and are suitable for bone cells, etc., while the products obtained in examples 3 to 4 have a low surface modulus and are suitable for nerve cells, etc. However, the content of the hydroxyapatite is not suitable to be too high, otherwise the structure of the starch/PVA and chitosan film layer can be damaged, and finally the mechanical property of the product is reduced.
In the invention, ceramic powder such as hydroxyapatite is dissolved in dopamine solution during preparation, and the surface of the hydroxyapatite is modified by utilizing dopamine autopolymerization technology so as to improve the dispersibility of the hydroxyapatite. After modification, the apparent particle size of the hydroxyapatite is reduced, and the dispersibility of the hydroxyapatite in water is greatly increased. As shown in comparative example 1, in the absence of dopamine, hydroxyapatite is added into the system, but due to poor dispersibility, the utilization rate of hydroxyapatite is extremely low, and the young modulus of the surface of the product is not obviously improved.
Aiming at the design of a formula, a matched process is adopted in the embodiment of the invention, after the first biological membrane is obtained, the first biological membrane is sequentially soaked by the chitosan solution and the auxiliary solution, the effects of various components are exerted to the maximum extent, and the degraded porous PVA/starch biological membrane is endowed with good mechanical property, surface Young modulus property and good biocompatibility. And finally, carrying out chemical crosslinking on the third biological membrane, thereby further improving the stability of the target biological membrane.
Other embodiments of the present invention than the preferred embodiments described above, and those skilled in the art can make various changes and modifications according to the present invention without departing from the spirit of the present invention, should fall within the scope of the present invention defined in the claims.
Claims (8)
1. A degradable porous PVA/starch biological film is characterized in that:
the paint comprises the following components in parts by weight:
100 parts of PVA;
10-50 parts of starch;
5-20 parts of chitosan;
5-20 parts of ceramic powder;
0.2-2 parts of dopamine;
0.1-1 part of a plasticizer;
0.1-1 part of a crosslinking agent;
wherein the chitosan has an average relative molecular mass of not less than 5 × 105The high molecular weight chitosan and the average relative molecular mass are not more than 1 x 104A mixture of low molecular weight chitosans of (a);
the preparation method of the degradable porous PVA/starch biological membrane comprises the following steps:
s1: adding the PVA, the starch and the plasticizer into water, stirring and dispersing, preparing a film forming solution with the mass fraction of 25-45% at 50-80 ℃, and then freezing and vacuumizing for reaction for 12-72 hours to obtain a first biological film;
s2: preparing the chitosan into a chitosan solution with the mass concentration not less than 3%, soaking the first biological membrane in the chitosan solution for 0.2-1 hour, and then cleaning with water to obtain a second biological membrane;
s3: dissolving the dopamine in a buffer solution, adding the ceramic powder, then vibrating and dispersing, reacting for 12-72 hours under stirring, and centrifuging to remove large particles to obtain an auxiliary solution;
s4: soaking the second biological membrane in the auxiliary solution for 0.2-1 hour, and then washing with water to obtain a third biological membrane;
s5: preparing the cross-linking agent into a cross-linking solution with the mass concentration not less than 1%, soaking the third biological membrane in the cross-linking solution for 5-10 hours, washing with water, and drying to obtain the degradable porous PVA/starch biological membrane.
2. The degradable porous PVA/starch biofilm of claim 1, wherein:
the ceramic powder is any one of hydroxyapatite, bioactive glass, calcium phosphate, alumina or zirconia.
3. The degradable porous PVA/starch biofilm of claim 1, wherein:
the plasticizer is at least one of glycerol, diglycerol, ethylene glycol, polyethylene glycol and propylene glycol.
4. The degradable porous PVA/starch biofilm of claim 1, wherein:
the cross-linking agent is any one of carbodiimide, sulphosuccinimide, glutaraldehyde, dimethylol urea and trimethylol melamine.
5. The degradable porous PVA/starch biofilm of claim 1, wherein:
the degradable porous PVA/starch biological membrane further comprises 0.1-1 part of auxiliary active ingredients.
6. The biodegradable porous PVA/starch biofilm of claim 5, wherein:
the auxiliary active component is at least one of inorganic antibacterial agent and tissue growth factor.
7. A degradable porous PVA/starch biofilm according to any one of claims 1 to 6, wherein:
the pH value of the buffer solution used in the step S3 is 8-9.
8. A degradable porous PVA/starch biofilm according to any one of claims 5 or 6, wherein:
further comprising the steps of:
and soaking the prepared degradable porous PVA/starch biological membrane in a solution containing the auxiliary active ingredient for 5-10 hours to obtain the degradable porous PVA/starch biological membrane loaded with the auxiliary active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110292801.XA CN113082299B (en) | 2021-03-18 | 2021-03-18 | Degradable porous PVA/starch biological membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110292801.XA CN113082299B (en) | 2021-03-18 | 2021-03-18 | Degradable porous PVA/starch biological membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113082299A CN113082299A (en) | 2021-07-09 |
| CN113082299B true CN113082299B (en) | 2022-07-08 |
Family
ID=76668340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110292801.XA Active CN113082299B (en) | 2021-03-18 | 2021-03-18 | Degradable porous PVA/starch biological membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113082299B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528717A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Coating agent for slow release fertilizer |
| CN101444636A (en) * | 2009-01-05 | 2009-06-03 | 北京化工大学 | Degradable multiporous faecula/PVA biological film and preparation method thereof |
| CN102138872A (en) * | 2011-03-03 | 2011-08-03 | 浙江大学 | Chitosan lotion and preparation method thereof |
| WO2013163704A1 (en) * | 2012-05-04 | 2013-11-07 | Bioactive Tecnologia Em Polímeros Ltda - Me | Porous bioactive and bioresorbable membrane and method for producing same |
| CN105079887A (en) * | 2015-06-18 | 2015-11-25 | 中国科学技术大学 | Blocky bionic material, method for manufacturing same and application of blocky bionic material |
| CN108546338A (en) * | 2018-04-04 | 2018-09-18 | 合肥市风达农业有限责任公司 | A kind of natural silk compound bio glass material preparation method |
| CN108794954A (en) * | 2018-05-28 | 2018-11-13 | 芜湖晋诚农业科技有限公司 | A kind of special polyvinyl alcohol film of vegetable and fruit packaging |
| CN109183127A (en) * | 2018-11-15 | 2019-01-11 | 长沙瑞联材料科技有限公司 | A kind of preparation method of Mg alloy surface carboxy apatite composite coating |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050058688A1 (en) * | 2003-02-22 | 2005-03-17 | Lars Boerger | Device for the treatment and prevention of disease, and methods related thereto |
| JP2006052480A (en) * | 2004-08-10 | 2006-02-23 | Nisshinbo Ind Inc | Method for processing cellulosic fiber-containing cloth and the cellulosic fiber-containing cloth |
| KR101853283B1 (en) * | 2012-11-14 | 2018-04-30 | 메드프린 리제너레이티브 메디컬 테크놀러지스 컴퍼니 리미티드 | Fibrous Membrane Used for Tissue Repair and Products and Preparation Methods Thereof |
| CN108395582B (en) * | 2018-04-11 | 2020-10-16 | 河北农业大学 | Cassava starch-polyvinyl alcohol-chitosan composite film and preparation method thereof |
| CN109908394A (en) * | 2019-02-26 | 2019-06-21 | 南京理工大学 | Degradable medical antibacterial leakage protection film and preparation method thereof |
-
2021
- 2021-03-18 CN CN202110292801.XA patent/CN113082299B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528717A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Coating agent for slow release fertilizer |
| CN101444636A (en) * | 2009-01-05 | 2009-06-03 | 北京化工大学 | Degradable multiporous faecula/PVA biological film and preparation method thereof |
| CN102138872A (en) * | 2011-03-03 | 2011-08-03 | 浙江大学 | Chitosan lotion and preparation method thereof |
| WO2013163704A1 (en) * | 2012-05-04 | 2013-11-07 | Bioactive Tecnologia Em Polímeros Ltda - Me | Porous bioactive and bioresorbable membrane and method for producing same |
| CN105079887A (en) * | 2015-06-18 | 2015-11-25 | 中国科学技术大学 | Blocky bionic material, method for manufacturing same and application of blocky bionic material |
| CN108546338A (en) * | 2018-04-04 | 2018-09-18 | 合肥市风达农业有限责任公司 | A kind of natural silk compound bio glass material preparation method |
| CN108794954A (en) * | 2018-05-28 | 2018-11-13 | 芜湖晋诚农业科技有限公司 | A kind of special polyvinyl alcohol film of vegetable and fruit packaging |
| CN109183127A (en) * | 2018-11-15 | 2019-01-11 | 长沙瑞联材料科技有限公司 | A kind of preparation method of Mg alloy surface carboxy apatite composite coating |
Non-Patent Citations (1)
| Title |
|---|
| 亲水改性剂表面修饰纳米羟基磷灰石对其分散性的影响;李刚等;《高分子材料科学与工程》;20181107(第10期);第67页第1.2节，第71页右栏第3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113082299A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Chitosan-based composite hydrogels for biomedical applications | |
| Shi et al. | Therapeutic potential of chitosan and its derivatives in regenerative medicine | |
| AU773826B2 (en) | Hyaluronic acid gel composition, process for producing the same, and medical material containing the same | |
| Shin et al. | In vivo bone and soft tissue response to injectable, biodegradable oligo (poly (ethylene glycol) fumarate) hydrogels | |
| Mathuriya et al. | Polyhydroxyalkanoates: biodegradable plastics and their applications | |
| Khor et al. | Implantable applications of chitin and chitosan | |
| AU2009202809B2 (en) | Functionalized inclusion complexes as crosslinkers | |
| US6514522B2 (en) | Polymer constructs | |
| Ke et al. | Surface modification of polyhydroxyalkanoates toward enhancing cell compatibility and antibacterial activity | |
| Nath et al. | Development of a gelatin‐g‐poly (acrylic acid‐co‐acrylamide)–montmorillonite superabsorbent hydrogels for in vitro controlled release of vitamin B12 | |
| WO2022012339A1 (en) | Method for constructing bone morphogenetic protein sustained-release system | |
| CN110152055B (en) | Functional drug sustained-release medical dressing constructed by alginic acid aminated derivative/bacterial cellulose nanocrystalline composite gel | |
| KR20000042641A (en) | Polyether grafted biodegradable aliphatic polyester and process of manufacture | |
| Zhou et al. | An antibacterial chitosan-based hydrogel as a potential degradable bio-scaffold for alveolar ridge preservation | |
| CN113082299B (en) | Degradable porous PVA/starch biological membrane and preparation method thereof | |
| Jiao et al. | Recent advances in strategies of nanocellulose surface and/or interface engineering for potential biomedical applications as well as its ongoing challenges: a review | |
| Hossain et al. | Poly (trimethylene carbonate-co-caprolactone): An emerging drug delivery nanosystem in pharmaceutics | |
| CN116376123A (en) | Injectable glucan-based hydrogel, glucan-based hydrogel loaded with paris polyphylla saponin I, and preparation method and application thereof | |
| Magagula et al. | Biopolymer-based biodegradable biomaterials for in vivo and in vitro biomedical applications | |
| KR20190114060A (en) | Biodegradable polymer hydrogel complex and method for producing the same | |
| Bunster | Polyhydroxyalkanoates: production and use | |
| CN113603855A (en) | Antibacterial polyurethane foam material and preparation method and application thereof | |
| Patil et al. | Hemicellulose-based delivery systems: Focus on pharmaceutical and biomedical applications | |
| Bombaldi de Souza et al. | Xanthan Gum for Regenerative Medicine | |
| Säilynoja et al. | Immobilization of a biologically active coating on a hydrophobic L-lactide-ɛ-caprolactone copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |