CN106750399B - A kind of selfreparing, photaesthesia aquagel and preparation method thereof - Google Patents

A kind of selfreparing, photaesthesia aquagel and preparation method thereof Download PDF

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CN106750399B
CN106750399B CN201611102643.2A CN201611102643A CN106750399B CN 106750399 B CN106750399 B CN 106750399B CN 201611102643 A CN201611102643 A CN 201611102643A CN 106750399 B CN106750399 B CN 106750399B
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aquagel
photaesthesia
selfreparing
nitro
chitosan
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CN106750399A (en
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张怀红
仓辉
孙柏旺
孙玉
蔡照胜
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Haiyang Qiji (Hainan) Biotechnology Co., Ltd
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Yangcheng Institute of Technology
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    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
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    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/44Medicaments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0015Medicaments; Biocides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0031Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/08Polysaccharides
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    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/00272-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C08J3/075Macromolecular gels
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
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    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

The present invention discloses a kind of selfreparing, photaesthesia aquagel and preparation method thereof; the preparation method of the aquagel includes: (1) using carboxymethyl chitosan and nitro dopamine as raw material progress acylation reaction, obtains the chitosan derivatives of the amine groups of DOPA containing nitro;(2) by the aqueous solution and Fe of the chitosan derivatives of the amine groups of DOPA containing nitro3+Solution mixing, adjusts the pH to 6.5~9.5 of mixed solution, obtains selfreparing, photaesthesia aquagel.The present invention uses mussel biomimetic chemistry method, and by crosslinking the chitosan derivatives for containing nitro DOPA amine groups with metallic ion coordination, dopamine has fine biocompatibility, reduces toxicity of the hydrogel to organism of conventional method preparation;Selfreparing obtained, photaesthesia aquagel adhesion is strong, compliance is good, space-time controllability is strong, as wound dressing, can maintain best moist environment for a long time on wound face, promote wound epithelialization, accelerating wound healing.

Description

A kind of selfreparing, photaesthesia aquagel and preparation method thereof
Technical field
The present invention relates to a kind of hydrogel and preparation method thereof, in particular to a kind of selfreparing, photaesthesia chitosan water-setting Glue and preparation method thereof.
Background technique
Chitosan is that unique positive linear polysaccharide, basic unit are gucosamine in nature, has bio-compatible Property it is good, have no toxic side effect, abundance the features such as, oneself food industry, synthesis of pharmaceutical preparation, medical macromolecular materials etc. lead Domain obtains extensive development and application.Based on different mechanism (covalently, ion, hydrogen bond), chitosan can form hydrogel, this is There are many relevant reports.Chitosan and glutaraldehyde etc. can form chemical gel, can also be with thioacetic acid, acrylic acid, grass Acid etc. forms physical gel.In addition chitosan and metal ion or other biological polymer (such as: going back virgin rubber, carragheen etc.) Forming ionic cross-linked bond by electrostatic interaction becomes gel.However, the formation of these aquagels is both needed to additionally incorporate Crosslinking agent such as glutaraldehyde etc., the use of crosslinking agent have the following deficiencies: that (1) is crosslinked due to glutaraldehyde and amino on chitosan It reacts extremely rapid, glutaraldehyde is caused to be difficult to be uniformly mixed with chitosan aqueous solution;(2) since solution viscosity is very big, it is difficult to System cross-linking reaction removes a large amount of bubble in solution before occurring, and causes inside gel there are a large amount of stomata, gel it is equal Even property is very poor, easily occurs in swelling process broken;(3) many drugs all have amino, if implement it is in situ carry medicine, easily with penta Dialdehyde reacts;(4) glutaraldehyde is toxic, and residual is harmful to the human body.
In order to eliminate using chemical cross-linking agent and many drawbacks of bring, the metal for not needing chemical cross-linking agent is coordinated The research of hydrogel has caused the very big concern of people.Coordination can make to form coordinate bond between macromolecule and metal ion And obtain hydrogel, this crosslinked action can rapidly and efficiently crosslink polymer molecules, and be formed by hydrogel tool There is self-repairability.Recently, mussel biomimetic chemistry causes the great interest of people, i.e., introduces catechu phenolic group in the side chain of polymer It rolls into a ball to obtain to occur the derivative of metal coordination, solution and metal ion (Fe3+、Ca2+、Ag+) coordination formed Hydrogel, but this hydrogel does not have light sensitivity, as bio-adhesive material, organizational project and controllable in drug release carrier Aspect application has significant limitation.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, the first object of the present invention is to provide a kind of selfreparing, light Sensitive aquagel, the hydrogel are free of any crosslinking agent, are provided simultaneously with self-repairability and light sensitivity, can be in ultraviolet lighting It penetrates down and is changed into the hydrosol;The second object of the present invention is to provide the preparation method of the aquagel.
Technical solution: selfreparing of the present invention, photaesthesia aquagel, molecular structural formula are as follows:
A kind of selfreparing of the present invention, photaesthesia aquagel preparation method, include the following steps:
(1) acylation reaction is carried out using carboxymethyl chitosan and nitro dopamine as raw material, obtains the amine groups of DOPA containing nitro Chitosan derivatives;
(2) by the aqueous solution and Fe of the chitosan derivatives of the amine groups of DOPA containing nitro3+Solution mixing, adjusts mixed solution PH to 6.5~9.5, obtain selfreparing, photaesthesia aquagel.
Specifically, carboxymethyl chitosan is dissolved in the water in step (1), it is more that nitro is added under inert gas protection Bar amine carries out acylation reaction, and dialysis, vacuum freeze drying, the chitosan for obtaining the amine groups of DOPA containing nitro spread out in water after reaction Biology.
Preferably, the ratio between molal quantity of the quality of the carboxymethyl chitosan of addition and nitro dopamine is 100:0.5~5.
The molecular weight M of above-mentioned carboxymethyl chitosannFor 10kDa~100kDa, degree of substitution DsIt is 0.3~0.5.
Preferably, combination catalyst is added in acylation reaction, which is N- hydroxysuccinimide and 1- second Base-(3- dimethylamino-propyl) carbodiimide.
Further, N- hydroxysuccinimide, 1- ethyl-(3- dimethylamino-propyl) carbodiimide and nitro dopamine Molar ratio be 0.5~5:0.5~5:0.5~5.
Above-mentioned acylation reaction carries out at room temperature, and the reaction time is 5~50h.
In above-mentioned steps (2), the concentration of the chitosan derivatives aqueous solution of the amine groups of DOPA containing nitro is 10~80mg/ ML, Fe3+Fe in solution3+Concentration be 5~150mmol/L.
Further, Fe3+Solution is Fe3+Acid solution, when reaction, make sol pH variation slowly, gel can be prevented It is too fast, influence its mechanical performance.
Inventive principle: firstly, amidation process occurs by the carboxyl of carboxymethyl chitosan and the amino of nitro dopamine The nitro DOPA amine groups with fine metal coordination ability and photaesthesia are introduced, reaction process such as following formula:
Then the chitosan derivatives of obtained DOPA containing nitro amine groups are crosslinked with metallic ion coordination, makes to make The aquagel obtained realizes self-repairability, meanwhile, dopamine has fine biocompatibility, so as to reduce hydrogel pair The toxicity of organism, finally obtained aquagel have bioadhesive, self-repairability and light sensitivity.
The utility model has the advantages that compared with the prior art, the advantages of the present invention are as follows: (1) selfreparing of the invention, photaesthesia shell are poly- Syrup gel has the characteristics that adhesion is strong, compliance is good, space-time controllability is strong, can be in wound face as wound dressing On maintain a best moist environment for a long time, promote cell migration, so as to promote the epithelialization of wound, accelerate wound The healing of mouth;(2) selfreparing of the invention, photaesthesia aquagel not only have self-repairability, also have light sensitivity, Under wavelength 365nm ultraviolet light, which can be changed into the hydrosol, as wound care dressings, organizational project Binder, drug controlled release carrier material have broad application prospects;(3) present invention change over by be chemically crosslinked come The method for preparing hydrogel, and the method for using mussel biomimetic chemistry, dopamine have fine biocompatibility, by the way that nitre will be contained The chitosan derivatives of Quito bar amine groups are crosslinked with metallic ion coordination, reduce the hydrogel pair of conventional method preparation The toxicity of organism.
Detailed description of the invention
Fig. 1 is the molecular structural formula of selfreparing of the invention, photaesthesia aquagel;
Fig. 2 is selfreparing of the invention, the metamorphosis figure of photaesthesia aquagel during the preparation process;
Fig. 3 is the metamorphosis figure of selfreparing of the invention, photaesthesia aquagel in self-repair procedure;
Fig. 4 is the metamorphosis figure of selfreparing of the invention, photaesthesia aquagel in the case where UV illumination is penetrated.
Specific embodiment
Technical solution of the present invention is described further with reference to the accompanying drawing.
Selfreparing of the invention, photaesthesia aquagel, molecular structural formula such as Fig. 1.
The selfreparing, photaesthesia aquagel preparation method include the following steps:
(1) using carboxymethyl chitosan and nitro dopamine as raw material, pass through the carboxyl and nitro DOPA of carboxymethyl chitosan It is that chitosan introduces the nitro DOPA amido with fine metal coordination ability and photaesthesia that amidation process, which occurs, for the amino of amine Group, obtains the chitosan derivatives of the amine groups of DOPA containing nitro;
(2) by the aqueous solution of the chitosan derivatives of the certain density amine groups of DOPA containing nitro and certain density Fe3+ Solution mixing, Fe3+Monodentate, bidentate and three tooth complexs, while Fe can be formed with dopamine3+Oxidation is also had both, so as to Obtain the aquagel with self-repairability and bioadhesive, such as Fig. 2.
Chitosan is native biopolymer, and source is extremely wide, safe and non-toxic, cheap, with synthesis macromolecule phase Than, there is good biocompatibility and biodegradability, therefore, using chitosan as raw material, aquagel obtained There is very high environment friendly and biological safety as wound dressing.
Embodiment 1
(1) chitosan derivatives of the amine groups of DOPA containing nitro are prepared
Take 100mg carboxymethyl chitosan (Mn=1.0 × 104Da, DS=0.3) it is dissolved in the deionized water of 50mL, logical 5mL hydroxysuccinimide Han 58mg (0.5mmol) N- (NHS) and 99mg (0.5mmol) nitro DOPA is added under nitrogen protection It is sub- to add 96mg (0.5mmol) 1- ethyl-(3- dimethylamino-propyl) carbon two for the DMF solution of amine disulfate (Mn=198) Amine (EDC), is stirred to react for 24 hours under room temperature.Two days, vacuum freeze drying of dialysis in deionized water obtain more containing nitro The chitosan derivatives of bar amine groups.
(2) selfreparing, photaesthesia aquagel are prepared
The chitosan derivatives of the amine groups of DOPA containing nitro of step (1) preparation are dissolved in 20mL water and obtain concentration and are The solution of 10mg/mL, with 5mL5mmol/L FeCl3Acetum is mixed, and the NaOH solution that 1mol/L is slowly added dropwise is adjusted The pH to 6.5 of solution, obtains filemot aquagel.
The performance of aquagel made from the present embodiment is detected, specific experiment method and test result is as follows One is tested to experiment four.
Experiment one: the self-repairability experiment of aquagel
Two parts of aquagels are made using step (1)~(2) method, then are close to place by them, it can by Fig. 3 To find out, after five minutes find two gels connect together, it is seen then that aquagel produced by the present invention have it is good from Prosthetic.
Experiment two: the photosensitivity experiment of aquagel
By aquagel made from step (2) with wavelength be 365nm, the UV illumination that power is 20W is penetrated, and has figure 4 as can be seen that irradiate after ten minutes, which becomes the hydrosol.
Experiment three: the water absorption rate experiment of aquagel
The aquagel being completely dried is cut into diamond type sample and is weighed.Then, sample is immersed in phosphoric acid Salt buffer (pH value 7.4;PBS), in specific time interval, i.e., sample is taken out into solution rapidly after 12 hours.With After paper handkerchief wipes sample, its weight is weighed, until stopping measurement after sample water suction saturation.The water absorption rate of aquagel is pressed Following formula are calculated:
Water absorption rate (%)=(Ws-Wd) × 100/Wd;
In formula, Wd represents weight when hydrogel drying, and Ws represents weight when hydrogel water suction is saturated.
The water absorption rate that experiment measures aquagel made from the present embodiment is 102%.
Experiment four: the adhesion strength experiment of aquagel
The fresh back normal skin tissue of pig is taken to cut into strips (4.0cm × 2.0cm, thick 1.5mm), by two pieces of skins Organize 2.0cm closely smooth on one side;The chitosan derivatives of the amine groups of DOPA containing nitro made from step (1) are dissolved to obtain Its aqueous solution (10mg/mL) takes 10 μ L chitosan aqueous solutions and 2 μ L Fe3+Solution mixing instills the adjacent sky of two skin histologies Gap, then the NaOH solution of 1mol/L is slowly instilled, it can be observed that gap gradually forms filemot aquagel.5 After minute, its adhesion strength is tested with mechanics tester.
The adhesion strength that experiment measures the aquagel of gap formation is 135.8kPa.
Embodiment 2
(1) chitosan derivatives of the amine groups of DOPA containing nitro are prepared
Take 100mg carboxymethyl chitosan (Mn=3.6 × 104Da, DS=0.4) it is dissolved in the deionized water of 50mL, logical It is more that 5mL hydroxysuccinimide Han 230mg (2.0mmol) N- (NHS) and 792mg (4.0mmol) nitro is added under nitrogen protection The DMF solution of bar amine disulfate (Mn=198), adds 384mg (2.0mmol) 1- ethyl-(3- dimethylamino-propyl) carbon Diimine (EDC), is stirred to react 5h under room temperature.Then in deionized water dialyse two days, vacuum freeze drying, contained The chitosan derivatives of nitro DOPA amine groups.
(2) selfreparing, the preparation of photaesthesia chitosan gel rubber
The chitosan derivatives of the amine groups of DOPA containing nitro of step (1) preparation are dissolved in 20mL water and obtain concentration and are 40mg/mL solution, the FeCl with 5mL80mmol/L3Acetum is mixed, and the NaOH solution that 1mol/L is slowly added dropwise is adjusted The pH of solution is 7.5, obtains filemot aquagel.
Experiment one: the self-repairability experiment of aquagel
Two parts of aquagels are made using step (1)~(2) method, then are close to place by them, after 7 minutes It was found that two gels connect together.
Experiment two: the photosensitivity experiment of aquagel
By aquagel made from step (2) with wavelength be 365nm, the UV illumination that power is 20W is penetrated, irradiation After 8 minutes, which becomes the hydrosol.
Experiment three: the water absorption rate experiment of aquagel
Referring to the water absorption rate test method in embodiment 1, the water absorption rate of aquagel made from the present embodiment is measured It is 96.8%.
Experiment four: the adhesion strength experiment of aquagel
Referring to the adhesion strength testing method of embodiment 1, with the amido of DOPA containing nitro made from step in the present embodiment (1) The chitosan derivatives of group form aquagel close to gap in two skin histologies for raw material, and the shell for measuring formation is poly- The adhesion strength of syrup gel, testing the adhesion strength measured is 141.5kPa.
Embodiment 3
(1) chitosan derivatives of the amine groups of DOPA containing nitro are prepared
Take 100mg carboxymethyl chitosan (Mn=5 × 104Da, DS=0.4) it is dissolved in the deionized water of 50mL, in logical nitrogen 10mL hydroxysuccinimide Han 345mg (3.0mmol) N- (NHS) and 990mg (5.0mmol) nitro DOPA is added under gas shielded The DMF solution of amine disulfate adds 576mg (3.0mmol) 1- ethyl-(3- dimethylamino-propyl) carbodiimide (EDC), It is stirred to react 50h under room temperature.Then in deionized water dialyse two days, vacuum freeze drying, obtain dopamine containing nitro The chitosan derivatives of group.
(2) selfreparing, the preparation of photaesthesia chitosan gel rubber
The chitosan derivatives of the amine groups of DOPA containing nitro of step (1) preparation are dissolved in 20mL water and obtain concentration and are 80mg/mL solution, the FeCl with 5mL100mmol/L3Acetum is mixed, and the NaOH solution tune of 1mol/L is slowly added dropwise The pH for saving solution is 8.5, obtains filemot aquagel.
Self-repairability experiment and photosensitivity experiment, experimental result and embodiment 1 are carried out to aquagel obtained Close, the aquagel obtained has good self-repairability and photosensitivity.
Referring to the water absorption rate test method and adhesion strength testing method in embodiment 1, shell made from the present embodiment is measured The water absorption rate of glycan hydrogel is 113.7%, adhesion strength 121.4kPa.
Embodiment 4
(1) chitosan derivatives of the amine groups of DOPA containing nitro are prepared
Take 100mg carboxymethyl chitosan (Mn=10 × 104Da, DS=0.5) it is dissolved in the deionized water of 50mL, logical 5mL hydroxysuccinimide Han 575mg (5mmol) N- (NHS) and 990mg (5mmol) nitro dopamine is added under nitrogen protection The DMF solution of disulfate (Mn=198) adds 910mg (5mmol) 1- ethyl-(3- dimethylamino-propyl) carbodiimide (EDC), it is stirred to react 50h under room temperature.Then it dialyses two days, vacuum freeze drying, is obtained containing nitro in deionized water The chitosan derivatives of DOPA amine groups.
(2) selfreparing, the preparation of photaesthesia chitosan gel rubber
The chitosan derivatives of the amine groups of DOPA containing nitro of step (1) preparation are dissolved in 25mL water and obtain concentration and are 80mg/mL solution, the FeCl with 5mL150mmol/L3Acetum is mixed, and the NaOH solution tune of 1mol/L is slowly added dropwise The pH for saving solution is 9.5, obtains filemot aquagel.
Self-repairability experiment and photosensitivity experiment, experimental result and embodiment 1 are carried out to aquagel obtained Close, the aquagel obtained has good self-repairability and photosensitivity.
Referring to the water absorption rate test method and adhesion strength testing method in embodiment 1, shell made from the present embodiment is measured The water absorption rate of glycan hydrogel is 116.3%, adhesion strength 137.5kPa.
Influence of the amount of 5 nitro dopamine of embodiment to aquagel performance obtained
Referring to the method for embodiment 1,5 groups of parallel laboratory tests are carried out, difference is the nitro dopamine being added in step (1) Amount is respectively 0.1mmol, 0.5mmol, 3mmol, 5mmol and 7mmol, the performance such as following table of final aquagel obtained 1。
The performance of aquagel made from different amounts of nitro dopamine is added in table 1
As can be seen from Table 1, the amount for the nitro dopamine being added in acylation reaction directly affects the chitosan water-setting to be formed Self-healing properties, water imbibition and the adhesiveness of glue, when the quality of the carboxymethyl chitosan of addition and the molal quantity of nitro dopamine The ratio between be 100:0.5~5 when, the selfreparing gelation time of aquagel is obviously shortened, only 5~6min, meanwhile, Water imbibition and adhesiveness are obviously improved, and water absorption rate reaches 102%~107%, and adhesion strength reaches 135.8~141kpa, can be with It is preferably attached on the surface of a wound, and maintains a best moist environment for a long time on wound face, accelerate the healing of wound.
Influence of the degree of substitution of 6 carboxymethyl chitosan of embodiment to aquagel performance obtained
Referring to the method for embodiment 1,5 groups of parallel laboratory tests are carried out, difference is the substitution of carboxymethyl chitosan in step (1) Degree is respectively 0.2,0.3,0.4,0.5 and 0.6, performance such as the following table 2 of final aquagel obtained.
Table 2 is using the carboxymethyl chitosan of different degree of substitution as the performance of aquagel made from raw material
As shown in Table 2, the degree of substitution of carboxymethyl chitosan is also an important factor for influencing aquagel performance, to be elected to When the degree of substitution of the carboxymethyl chitosan taken is 0.3~0.5, the self-repairability of the aquagel of formation, water imbibition and viscous Attached property reaches most strong, and selfreparing gelation time is only 5~6min, meanwhile, water absorption rate is 102%~112%, is sticked Intensity is 135.8~142kpa, is had excellent performance as wound care dressings, organizational project binder etc.;When carboxymethyl shell The degree of substitution of glycan is greater than 0.5 or when less than 0.3, and the self-repairability of the aquagel of formation, water imbibition and adhesiveness are equal Substantially weaken.

Claims (8)

1. a kind of selfreparing, photaesthesia aquagel, which is characterized in that the molecular formula of the aquagel is
The preparation method of the aquagel includes the following steps:
(1) acylation reaction is carried out using carboxymethyl chitosan and nitro dopamine as raw material, obtains the shell of the amine groups of DOPA containing nitro Polysaccharid derivative;The molecular weight M of the carboxymethyl chitosannFor 10kDa~100kDa, degree of substitution DsIt is 0.3~0.5;
(2) by the aqueous solution and Fe of the chitosan derivatives of the amine groups of DOPA containing nitro3+Solution mixing, adjusts the pH of mixed solution To 6.5~9.5, selfreparing, photaesthesia aquagel are obtained.
2. selfreparing according to claim 1, photaesthesia aquagel, which is characterized in that in step (1), by carboxylic Methyl chitosan is dissolved in the water, and nitro dopamine is added under inert gas protection and carries out acylation reaction, after reaction in water Dialysis, vacuum freeze drying, obtain the chitosan derivatives of the amine groups of DOPA containing nitro.
3. selfreparing according to claim 1 or 2, photaesthesia aquagel, which is characterized in that the carboxymethyl shell The ratio between the quality of glycan and the molal quantity of nitro dopamine are 100:0.5~5.
4. selfreparing according to claim 1 or 2, photaesthesia aquagel, which is characterized in that the acylation reaction Middle addition combination catalyst, the combination catalyst are N- hydroxysuccinimide and 1- ethyl-(3- dimethylamino-propyl) carbon two Imines.
5. selfreparing according to claim 4, photaesthesia aquagel, which is characterized in that the N- hydroxyl fourth two The molar ratio of acid imide, 1- ethyl-(3- dimethylamino-propyl) carbodiimide and nitro dopamine is 0.5~5:0.5~5:0.5 ~5.
6. selfreparing according to claim 1, photaesthesia aquagel, which is characterized in that the acylation reaction exists It carries out under room temperature, the reaction time is 5~50h.
7. selfreparing according to claim 1, photaesthesia aquagel, which is characterized in that described in step (2) The concentration of the chitosan derivatives aqueous solution of the amine groups of DOPA containing nitro is 10~80mg/mL, Fe3+Fe in solution3+Concentration be 5~150mmol/L.
8. selfreparing according to claim 1, photaesthesia aquagel, which is characterized in that the Fe3+Solution is Fe3+Acid solution.
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