CN113683786B - Double self-healing antibacterial hydrogel and preparation method and application thereof - Google Patents
Double self-healing antibacterial hydrogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN113683786B CN113683786B CN202110888985.6A CN202110888985A CN113683786B CN 113683786 B CN113683786 B CN 113683786B CN 202110888985 A CN202110888985 A CN 202110888985A CN 113683786 B CN113683786 B CN 113683786B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- quaternary ammonium
- ammonium salt
- solution
- chitosan quaternary
- 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
- 239000000017 hydrogel Substances 0.000 title claims abstract description 84
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001661 Chitosan Polymers 0.000 claims abstract description 99
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 90
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 90
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 35
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 229920002085 Dialdehyde starch Polymers 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 17
- 239000004327 boric acid Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 230000009977 dual effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 241001391944 Commicarpus scandens Species 0.000 abstract description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 4
- 241000894006 Bacteria Species 0.000 abstract description 3
- 230000035876 healing Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- 239000003814 drug Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 241000192125 Firmicutes Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000002289 effect on microbe Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/10—Oxidised starch
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/38—Boron-containing compounds
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a double self-healing antibacterial hydrogel and a preparation method and application thereof, wherein the O site on chitosan is quaternized, so that the original amino is reserved, and a quaternary ammonium group with positive charges is added, so that chitosan molecules have double antibacterial groups, and graphene oxide is compounded, so that the double self-healing antibacterial hydrogel has good antibacterial performance on gram positive and negative bacteria, and meanwhile, the mechanical property and the thermal property of the hydrogel are improved. In addition, a double self-healing network structure of the O-chitosan quaternary ammonium salt and the polyvinyl alcohol is constructed, so that a double healing effect is realized, and the self-healing effect of the hydrogel is remarkably improved; meanwhile, the problems that the chitosan hydrogel is brittle and is easy to break, and the traditional polyvinyl alcohol and chitosan hydrogel has no or insufficient antibacterial property are effectively solved.
Description
Technical Field
The invention relates to the technical field of biological medicine and personal hygiene materials, in particular to a double self-healing antibacterial hydrogel and a preparation method thereof.
Background
By self-healing material, it is meant that the material assembly is capable of continuously sensing and responding to damage during the life of the material and automatically recovering the properties of the material without adversely affecting the properties of the original material, and self-healing will be beneficial for extending the life of the material. Among the self-healing materials, self-healing hydrogels based on polymers have attracted great attention and research interest due to the structural diversity and designability, and the adjustability of performance and function of the polymeric substrates. Wherein, when the implant material is used as an implant material, the implant material can heal and recover the function after being damaged accidentally. Therefore, the method is not only beneficial to prolonging the service life of the material, but also can reduce the extra operation brought by replacing the material.
In addition, self-healing hydrogels are also suitable for use in wound dressings. Compared with the traditional gauze, the hydrogel dressing provides a moist environment for the wound surface and is beneficial to wound healing. However, the moist environment of the hydrogel dressing provides good growth conditions for pathogenic microorganisms, and therefore the application of the hydrogel dressing requires consideration of its antimicrobial properties, whereas self-healing can spontaneously repair dressing lesions that occur during use.
Chitosan is prepared from chitosan by deacetylation. However, the strong hydrogen bond between chitosan molecules makes chitosan generally only soluble in acid solution, which makes chitosan difficult to process, thereby limiting the application range. The dissolving and antibacterial capacity of chitosan can be enhanced by introducing quaternary ammonium groups, the traditional chitosan quaternary ammonium salt is a product obtained by substituting N sites of chitosan, and many functional properties of chitosan are derived from amino groups, so that the original properties are weakened or lost after the amino groups are substituted. The simple polyvinyl alcohol hydrogel has no inhibition effect on microorganisms, which also limits the application of the simple polyvinyl alcohol hydrogel in biomedical materials.
The chitosan and the derivatives thereof have good biocompatibility and are important biomedical raw materials. In recent years, a large amount of chitosan and its derivative hydrogel have been developed, but the hydrogel is brittle in texture and insufficient in mechanical properties, and is easy to break in the use process, so that the hydrogel is inconvenient to replace frequently in the use process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a double self-healing antibacterial hydrogel and a preparation method and application thereof, wherein O-chitosan derivatives, polyvinyl alcohol and graphene oxide are compounded to form double-network double-crosslinked self-healing hydrogel, and O-chitosan derivatives are reacted with 2, 3-epoxypropyl trimethyl ammonium chloride to obtain retained-NH (NH) 2 The chitosan quaternary ammonium salt endows the chitosan with antibacterial property and keeps good self-functional characteristics of chitosan; the introduction of the graphene oxide simultaneously improves the mechanical property, antibacterial property and thermal property of the hydrogel. In order to achieve the aim, the raw materials of the self-healing antibacterial hydrogel comprise O-chitosan quaternary ammonium salt, polyvinyl alcohol, graphene oxide and a mixed cross-linking agent, wherein the dosage of the O-chitosan quaternary ammonium salt is 20-100% of the weight of the polyvinyl alcohol, the dosage of the graphene oxide is 1-13.3% of the weight of the polyvinyl alcohol, the mixed cross-linking agent consists of dialdehyde starch and boric acid, and the dosage of the mixed cross-linking agent is 3.4-17.2% of the weight of the polyvinyl alcohol.
The invention also provides a preparation method of the double self-healing antibacterial hydrogel, which comprises the following steps:
(1) Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
(2) Dissolving O-chitosan quaternary ammonium salt in water to obtain O-chitosan quaternary ammonium salt solution;
(3) Adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and uniformly mixing to prepare an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
(4) Ultrasonically dispersing graphene oxide in water to obtain graphene oxide dispersion liquid, adding the graphene oxide dispersion liquid into an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly mixing to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
(5) Preparing a mixed cross-linking agent from dialdehyde starch and boric acid;
(6) Mixing the composite solution in the step (4) with the mixed cross-linking agent in the step (5), preserving heat in a water bath, and obtaining the double self-healing antibacterial hydrogel after the cross-linking reaction is completed.
Further, in the step (1), a polyvinyl alcohol solution is prepared at a concentration of 0.04 to 0.12 g.multidot.mL -1 。
Still further, in the step (3), the O-chitosan quaternary ammonium salt solution is mixed with the polyvinyl alcohol solution in equal volume.
Still further, in the step (4), the volume of the graphene oxide dispersion liquid is 26.7% of the volume of the polyvinyl alcohol solution; in the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, the dosage of the O-chitosan quaternary ammonium salt is 20-100% of the mass of the polyvinyl alcohol, and the dosage of the graphene oxide is 1-13.3% of the mass of the polyvinyl alcohol.
Still further, in the step (5), a crosslinking agent is mixed, and the concentration of dialdehyde starch is 0.1 g.multidot.mL -1 Boric acid concentration of 0.003 g.mL -1 。
Still further, in the step (6), the volume of the mixed cross-linking agent is 2.7% -13.3% of the volume of the polyvinyl alcohol solution; and the dosage of the mixed cross-linking agent is 3.4-17.2 percent of the mass of the polyvinyl alcohol.
Still further, the temperature of the polyvinyl alcohol solution is prepared at 85-95 ℃.
Still further, the water bath heat preservation temperature is 35-45 ℃, and the reaction time is 12-24 hours.
The invention also provides application of the double self-healing antibacterial hydrogel in preparation of biological medicines and personal hygiene materials.
The preparation mechanism of the double self-healing antibacterial hydrogel comprises the following steps:
the O-chitosan quaternary ammonium salt causes the chitosan molecule to have double antibacterial groups (amino groups and quaternary ammonium groups) by quaternizing the oxygen sites on the chitosan. The introduction of the graphene oxide can simultaneously improve the mechanical property, the antibacterial property and the thermal property of the hydrogel. Under the condition that the graphene oxide is dispersed in the O-chitosan quaternary ammonium salt and the polyvinyl alcohol, a bi-component and bi-crosslinked network structure is formed simultaneously, namely, the O-chitosan quaternary ammonium salt self-healing network and the polyvinyl alcohol self-healing network are not independent, but mutually intersected, cross-linking is formed through hydrogen bonding, the graphene oxide is loaded in the dual network structure through hydrogen bonding, and a scanning electron microscope result of the dual self-healing antibacterial hydrogel is shown in a figure 1, so that a novel and stable three-dimensional network structure is finally formed.
The invention has the beneficial effects that:
1. the hydrogel provided by the invention has excellent self-healing, antibacterial and mechanical properties. Simple chitosan hydrogel is brittle and is easy to break; the conventional polyvinyl alcohol hydrogel does not have antibacterial properties, but rather provides an effective carbon source and a good microenvironment to promote bacterial growth, which seriously affects the use effect and limits its application. Compared with the prior chitosan or N-chitosan quaternary ammonium salt hydrogel, the invention retains the original amino group and adds the quaternary ammonium group with positive charge by quaternizing the oxygen position on the chitosan, so that the chitosan molecule has double antibacterial groups, and the graphene oxide is compounded, so that the chitosan has good antibacterial performance on gram-positive bacteria and gram-negative bacteria; in addition, a double self-healing network structure of the O-chitosan quaternary ammonium salt and the polyvinyl alcohol is constructed, so that a double healing effect is realized, the self-healing effect of the hydrogel is obviously improved, and the service life is prolonged; meanwhile, the double cross-linked network structure of the two high polymer components and the composite graphene oxide obviously enhance the mechanical strength of the hydrogel, and effectively solve the problems that the chitosan hydrogel is relatively brittle and is easy to break, and the traditional polyvinyl alcohol and chitosan hydrogel has no antibacterial property or insufficient antibacterial property.
2. The dual self-healing antibacterial hydrogel disclosed by the invention has the advantage that the mechanical property is improved by 3-4 times along with the addition of graphene oxide.
3. The double self-healing antibacterial hydrogel is different from other single-network hydrogels, and has a double-network structure, so that the hydrogel structure is more stable.
4. The double self-healing antibacterial hydrogel realizes double self-healing effect through the double cross-linked network of polyvinyl alcohol and chitosan quaternary ammonium salt, has more reliable self-healing performance, can adapt to different application environments, and overcomes the problem that a single self-healing structure has an unsatisfactory self-healing effect under certain environments.
5. The dual self-healing antibacterial hydrogel provided by the invention has obvious swelling effect. The chitosan has poor self-hydrophilicity, and the hydrophilicity is obviously improved after quaternization, so that the equilibrium swelling rate of the hydrogel reaches 720%.
6. The dual self-healing antibacterial hydrogel has good antibacterial performance on staphylococcus aureus and escherichia coli, and the antibacterial performance of the dual self-healing antibacterial hydrogel can be obviously improved by introducing graphene oxide.
7. The dual self-healing antibacterial hydrogel can realize flexible control of swelling, mechanics and antibacterial performance through adjustment of technological parameters.
8. The double self-healing antibacterial hydrogel can be loaded with drugs and used as a drug release carrier.
9. The dialdehyde starch crosslinking agent used in the invention is safer and more stable and has good biocompatibility.
Drawings
FIG. 1 is a scanning electron microscope image of a dual self-healing antimicrobial hydrogel;
FIG. 2 is a graph of the self-healing properties of a dual self-healing antimicrobial hydrogel.
Detailed Description
The present invention is described in further detail below in conjunction with specific embodiments for understanding by those skilled in the art.
Example 1
1) Stirring and dissolving 0.27-g O-chitosan quaternary ammonium salt in 7.5mL of deionized water at room temperature to obtain an O-chitosan quaternary ammonium salt solution;
2) Stirring 0.45g of polyvinyl alcohol in a water bath at 90 ℃ to dissolve in 7.5mL of deionized water to obtain a polyvinyl alcohol solution; adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and rapidly and uniformly stirring to obtain an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
3) Taking 0.02g of graphene oxide in 2mL of water, uniformly dispersing by ultrasonic, adding the graphene oxide into the O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly stirring to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
4) Preparing a mixed cross-linking agent of dialdehyde starch and boric acid, wherein the concentration of dialdehyde starch is 0.1 g.mL -1 Boric acid concentration of 0.003 g.mL -1 ；
5) And adding 0.4mL of the mixed cross-linking agent into the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, rapidly and uniformly stirring, and heating the reaction solution to 40 ℃ for water bath reaction for 16 hours to obtain the double self-healing antibacterial hydrogel 1.
The self-healing performance of the double self-healing antibacterial hydrogel 1 obtained by the method is shown in figure 2, and the self-healing interface of the hydrogel is free of cracks through stretching and twisting after the hydrogel is cut and self-healed, so that the gel has excellent self-healing performance. The equilibrium swelling of the hydrogels obtained according to the invention in pure water was 666%.
Example 2
1) Stirring and dissolving 0.48-g O-chitosan quaternary ammonium salt in 7.5mL of deionized water at room temperature to obtain an O-chitosan quaternary ammonium salt solution;
2) Stirring 0.6g of polyvinyl alcohol in a water bath at 90 ℃ to dissolve in 7.5mL of deionized water to obtain a polyvinyl alcohol solution; adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and rapidly and uniformly stirring to obtain an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
3) Taking 0.02g of graphene oxide in 2mL of water, uniformly dispersing by ultrasonic, adding the graphene oxide into the O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly stirring to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
4) Preparing a mixed cross-linking agent of dialdehyde starch and boric acid, wherein the concentration of dialdehyde starch is 0.1 g.mL -1 Boric acid concentration of 0.003 g.mL -1 ；
5) And adding 0.4mL of the mixed cross-linking agent into the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, rapidly and uniformly stirring, and heating the reaction solution to 40 ℃ for water bath reaction for 16 hours to obtain the double self-healing antibacterial hydrogel 2.
The hydrogel 2 obtained by the method has good antibacterial performance, the antibacterial rate of the hydrogel to staphylococcus aureus (gram-positive bacteria) is 67.2%, and the antibacterial rate to escherichia coli (gram-negative bacteria) is 58.5%. The equilibrium swelling of the hydrogels obtained according to the invention in pure water was 446%.
Example 3
1) Stirring and dissolving 0.36g O-chitosan quaternary ammonium salt in 7.5mL of deionized water at room temperature to obtain an O-chitosan quaternary ammonium salt solution;
2) Stirring 0.6g of polyvinyl alcohol in a water bath at 90 ℃ to dissolve in 7.5mL of deionized water to obtain a polyvinyl alcohol solution; adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and rapidly and uniformly stirring to obtain an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
3) Taking 0.06g of graphene oxide in 2mL of water, uniformly dispersing by ultrasonic, adding the graphene oxide into the O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly stirring to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
4) Preparing a mixed cross-linking agent solution of dialdehyde starch and boric acid, wherein the concentration of dialdehyde starch is 0.1 g.mL -1 Boric acid concentration of 0.003 g.mL -1 ；
5) And adding 0.4mL of mixed cross-linking agent solution into the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, rapidly and uniformly stirring, and heating the reaction solution to 40 ℃ for water bath reaction for 16 hours to obtain the double self-healing antibacterial hydrogel 3.
The hydrogel 3 obtained by the method has good mechanical property, and the compressive strength of the hydrogel is up to 1500Pa and 4 times of the compressive strength (390 Pa) of the hydrogel without graphene oxide; in addition, the fastest weight loss temperature of the hydrogel obtained by the method is 308 ℃, and the fastest weight loss temperature of the hydrogel without graphene oxide is 238 ℃, which shows that the introduction of the graphene oxide improves the thermal decomposition temperature and the thermal stability of the hydrogel. The equilibrium swelling of the hydrogels obtained according to the invention in pure water was 468%. In addition, under the same process conditions, the antibacterial performance of the hydrogel can be improved along with the increase of the dosage of the graphene oxide, and when the dosage of the graphene oxide is 0.08g, the antibacterial rate is 1.92 times (staphylococcus aureus) and 1.57 times (escherichia coli) that of the hydrogel without the graphene oxide.
Example 4
1) Stirring and dissolving 0.18-g O-chitosan quaternary ammonium salt in 7.5mL of deionized water at room temperature to obtain an O-chitosan quaternary ammonium salt solution;
2) Stirring 0.3g of polyvinyl alcohol in a water bath at 90 ℃ to dissolve in 7.5mL of deionized water to obtain a polyvinyl alcohol solution; adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and rapidly and uniformly stirring to obtain an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
3) Taking 0.02g of graphene oxide in 2mL of water, uniformly dispersing by ultrasonic, adding the graphene oxide into the O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly stirring to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
4) Preparing a mixed cross-linking agent solution of dialdehyde starch and boric acid, wherein the concentration of dialdehyde starch is 0.1 g.mL -1 Boric acid concentration of 0.003 g.mL -1 ；
5) And adding 0.4mL of mixed cross-linking agent solution into the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, rapidly and uniformly stirring, and heating the reaction solution to 40 ℃ for water bath reaction for 16 hours to obtain the double self-healing antibacterial hydrogel 4.
The equilibrium swelling of the hydrogel 4 obtained by the method in pure water is 720%, the swelling performance is good, and the equilibrium swelling results combined with other examples show that the equilibrium swelling of the hydrogel can be regulated and controlled by the preparation process parameters.
Example 5
1) Stirring and dissolving 0.36g O-chitosan quaternary ammonium salt in 7.5mL of deionized water at room temperature to obtain an O-chitosan quaternary ammonium salt solution;
2) Stirring 0.6g of polyvinyl alcohol in a water bath at 90 ℃ to dissolve in 7.5mL of deionized water to obtain a polyvinyl alcohol solution; adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and rapidly and uniformly stirring to obtain an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
3) Taking 0.02g of graphene oxide in 2mL of water, uniformly dispersing by ultrasonic, adding the graphene oxide into the O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly stirring to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
4) Preparing a mixed cross-linking agent solution of dialdehyde starch and boric acid, wherein the concentration of dialdehyde starch is 0.1 g.mL -1 Boric acid concentration of 0.003 g.mL -1 ；
5) And adding 0.4mL of mixed cross-linking agent solution into the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution, rapidly and uniformly stirring, and heating the reaction solution to 40 ℃ for water bath reaction for 16 hours to obtain the double self-healing antibacterial hydrogel 5.
The equilibrium swelling of the hydrogel 5 obtained by the above method in pure water was 597%; when bovine serum albumin is added in step 1), the dual self-healing antibacterial hydrogel loaded with bovine serum albumin can be obtained, the dual self-healing antibacterial hydrogel is soaked in a phosphoric acid buffer solution (pH 7.4), and is oscillated at a constant temperature of 37 ℃ to release 70% in 4 hours and is basically completely released in 30 hours, so that the obtained hydrogel is suitable for being used as a drug carrier, and the drug release performance can be adjusted through preparation process parameters.
Other parts not described in detail are prior art. Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A double self-healing antibacterial hydrogel is characterized in that the raw materials of the self-healing antibacterial hydrogel compriseOChitosan quaternary ammonium salt, polyvinyl alcohol, graphene oxide and a mixed cross-linking agent, wherein,Othe dosage of the chitosan quaternary ammonium salt is 20% -100% of the mass of the polyvinyl alcohol, the dosage of the graphene oxide is 1% -13.3% of the mass of the polyvinyl alcohol, the mixed cross-linking agent consists of dialdehyde starch and boric acid, and the dosage of the mixed cross-linking agent is 3.4% -17.2% of the mass of the polyvinyl alcohol; the double self-healing antibacterial hydrogel is prepared by the following steps:
(1) Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
(2) Dissolving O-chitosan quaternary ammonium salt in water to obtain O-chitosan quaternary ammonium salt solution;
(3) Adding the polyvinyl alcohol solution into the O-chitosan quaternary ammonium salt solution, and uniformly mixing to prepare an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
(4) Ultrasonically dispersing graphene oxide in water to obtain graphene oxide dispersion liquid, adding the graphene oxide dispersion liquid into an O-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution, and uniformly mixing to obtain the O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
(5) Preparing a mixed cross-linking agent from dialdehyde starch and boric acid;
(6) Mixing the composite solution in the step (4) with the mixed cross-linking agent in the step (5), preserving heat in a water bath, and obtaining the double self-healing antibacterial hydrogel after the cross-linking reaction is completed.
2. A method for preparing the double self-healing antibacterial hydrogel according to claim 1, which comprises the following steps:
(1) Dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution;
(2) Will beODissolving chitosan quaternary ammonium salt in water to obtainO-chitosan quaternary ammonium salt solution;
(3) Adding polyvinyl alcohol solutionOMixing chitosan quaternary ammonium salt solution to prepareO-chitosan quaternary ammonium salt/polyvinyl alcohol composite solution;
(4) Ultrasonically dispersing graphene oxide in water to obtain graphene oxide dispersion liquid, and then adding the graphene oxide dispersion liquid into waterOMixing the mixture with chitosan quaternary ammonium salt/polyvinyl alcohol composite solution to obtainO-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution;
(5) Preparing a mixed cross-linking agent from dialdehyde starch and boric acid;
(6) Mixing the composite solution in the step (4) with the mixed cross-linking agent in the step (5), preserving heat in a water bath, and obtaining the double self-healing antibacterial hydrogel after the cross-linking reaction is completed.
3. The preparation method according to claim 2, characterized in that: the steps ofIn the step (1), the concentration of the polyvinyl alcohol solution is 0.04-0.12 g.mL −1 。
4. A method of preparation according to claim 3, characterized in that: in the step (3), the step of (c),Othe chitosan quaternary ammonium salt solution is mixed with the polyvinyl alcohol solution in equal volume.
5. The method of manufacturing according to claim 4, wherein: in the step (4), the volume of the graphene oxide dispersion liquid is 26.7% of the volume of the polyvinyl alcohol solution;Oin the chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide composite solution,Othe dosage of the chitosan quaternary ammonium salt is 20-100% of the mass of the polyvinyl alcohol, and the dosage of the graphene oxide is 1-13.3% of the mass of the polyvinyl alcohol.
6. The method of manufacturing according to claim 5, wherein: in the step (5), a cross-linking agent is mixed, and the concentration of dialdehyde starch is 0.1g mL −1 Boric acid concentration of 0.003g mL −1 。
7. The method of manufacturing according to claim 6, wherein: in the step (6), the volume of the mixed cross-linking agent is 2.7% -13.3% of the volume of the polyvinyl alcohol solution; and the dosage of the mixed cross-linking agent is 3.4-17.2% of the mass of the polyvinyl alcohol.
8. The preparation method according to claim 2, characterized in that: the temperature of the prepared polyvinyl alcohol solution is 85-95 ℃.
9. The preparation method according to claim 2, characterized in that: the water bath heat preservation temperature is 35-45 ℃, and the reaction time is 12-24 hours.
10. Use of the dual self-healing antimicrobial hydrogel of claim 1 in the preparation of biomedical and personal hygiene materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888985.6A CN113683786B (en) | 2021-08-03 | 2021-08-03 | Double self-healing antibacterial hydrogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888985.6A CN113683786B (en) | 2021-08-03 | 2021-08-03 | Double self-healing antibacterial hydrogel and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113683786A CN113683786A (en) | 2021-11-23 |
| CN113683786B true CN113683786B (en) | 2023-12-12 |
Family
ID=78578717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110888985.6A Active CN113683786B (en) | 2021-08-03 | 2021-08-03 | Double self-healing antibacterial hydrogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113683786B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539695B (en) * | 2021-12-14 | 2023-08-22 | 中国药科大学 | Muscle fiber-imitated high-toughness antibacterial healing-promoting hydrogel and preparation method and application thereof |
| CN115121192B (en) * | 2022-07-25 | 2023-05-26 | 中北大学 | Preparation method and application of PVA/HACC piezoelectric hydrogel of liquid metal/reduced graphene oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902778A (en) * | 2017-04-28 | 2017-06-30 | 武汉理工大学 | A kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof |
| CN107868261A (en) * | 2017-12-05 | 2018-04-03 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application |
| CN108853572A (en) * | 2018-06-01 | 2018-11-23 | 湖南国盛石墨科技有限公司 | Modified composite hydrogel of a kind of graphene oxide and its preparation method and application |
| CN110790885A (en) * | 2019-08-30 | 2020-02-14 | 武汉理工大学 | Polyvinyl alcohol/chitosan quaternary ammonium salt antibacterial self-healing hydrogel and preparation method and application thereof |
-
2021
- 2021-08-03 CN CN202110888985.6A patent/CN113683786B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902778A (en) * | 2017-04-28 | 2017-06-30 | 武汉理工大学 | A kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof |
| CN107868261A (en) * | 2017-12-05 | 2018-04-03 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application |
| CN108853572A (en) * | 2018-06-01 | 2018-11-23 | 湖南国盛石墨科技有限公司 | Modified composite hydrogel of a kind of graphene oxide and its preparation method and application |
| CN110790885A (en) * | 2019-08-30 | 2020-02-14 | 武汉理工大学 | Polyvinyl alcohol/chitosan quaternary ammonium salt antibacterial self-healing hydrogel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113683786A (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113683786B (en) | Double self-healing antibacterial hydrogel and preparation method and application thereof | |
| Chen et al. | Novel poly (vinyl alcohol)/chitosan/modified graphene oxide biocomposite for wound dressing application | |
| CN110117369B (en) | Antibacterial adhesive conductive hydrogel and preparation method and application thereof | |
| US20170014543A1 (en) | HYDROGEL BASED ON γ-POLYGLUTAMIC ACID AND ε-POLYLYSINE CROSSLINKED POLYMER, AND PREPARATION METHOD THEREFOR | |
| CN111154149A (en) | Hydrogel and preparation method and dressing thereof | |
| CN112480434B (en) | Copper ion antibacterial hydrogel and preparation method and application thereof | |
| CN107987439B (en) | Polyvinyl alcohol-based antibacterial hydrogel and preparation method and application thereof | |
| CN112851951B (en) | Dialdehyde chitosan grafted with epsilon-polylysine and preparation method and application thereof | |
| CN112451738B (en) | Silver ion polysaccharide polymer antibacterial dressing and preparation method and application thereof | |
| CN112647193B (en) | Preparation method of electron beam irradiation crosslinked calcium peroxide-carbon quantum dot @ zein antibacterial film | |
| CN110747534A (en) | Antibacterial polysaccharide fiber material and preparation method thereof | |
| CN113999406B (en) | Preparation method and application of multifunctional antibacterial hydrogel dressing | |
| US20210015966A1 (en) | Antibacterial Cellulose Hydrogels and Preparation Method therefor | |
| CN110152049B (en) | Application of chitosan-based nanofiber membrane of medical wound dressing | |
| CN114767923B (en) | Composite hydrogel silver-loaded long-acting antibacterial dressing and preparation method and application thereof | |
| CN115105629B (en) | Antibacterial hydrogel and preparation method and application thereof | |
| CN116407674A (en) | Preparation method of tannic acid-loaded high-strength self-healing antibacterial hydrogel | |
| Switha et al. | Fabrication of conductive hybrid scaffold based on polyaniline/polyvinyl alcohol–chitosan nanoparticles for skin tissue engineering application | |
| CN116769185A (en) | Preparation method of alginic acid antibacterial gel, product and application thereof | |
| CN115624647A (en) | Biological film medical dressing compounded with wound healing medicine and film essence, and preparation method and application thereof | |
| CN112791100A (en) | Composite antibacterial microsphere with efficient active oxygen scavenging function and preparation method thereof | |
| CN114796582A (en) | Preparation method of bacteriostatic gel containing graphene oxide | |
| CN112472867A (en) | Antibacterial medical hydrogel dressing and preparation method thereof | |
| CN113817232B (en) | Hydrogel and preparation method and application thereof | |
| CN116082694B (en) | Sponge compound for tissue wound repair and preparation method thereof |
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 |