CN110172163A - A method of fibroin albumen-tyrasamine modified hyaluronic acid hydrogel material is prepared based on physical-chemical double cross connection - Google Patents
A method of fibroin albumen-tyrasamine modified hyaluronic acid hydrogel material is prepared based on physical-chemical double cross connection Download PDFInfo
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- CN110172163A CN110172163A CN201910534888.XA CN201910534888A CN110172163A CN 110172163 A CN110172163 A CN 110172163A CN 201910534888 A CN201910534888 A CN 201910534888A CN 110172163 A CN110172163 A CN 110172163A
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- tyrasamine
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- fibroin albumen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/26—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
Fibroin albumen-tyrasamine modified hyaluronic acid hydrogel material method is prepared based on physical-chemical double cross connection the invention discloses a kind of, the method utilize two kinds of base stocks of fibroin albumen and tyrasamine modified hyaluronic acid (HA-Tyr), by be chemically crosslinked and be physical crosslinking the method combined be prepared with can gel in-situ, excellent biocompatibility and high-strength and high ductility fibroin albumen-hyaluronic acid gel.The technical program designs tissue engineering bracket material and prepares with reference significance.
Description
Technical field
The invention belongs to tissue engineering material fields, and in particular to one kind prepares fibroin egg based on physical-chemical double cross connection
The method of white-tyrasamine modified hyaluronic acid hydrogel material.
Background technique
Hydrogel is a kind of by the appropriately crosslinked novel high polymer material that 3 D stereo network structure is presented in space.By
In the presence of cross-linked structure, without dissolving, it is superpower that unique polymer network structure assigns its for hydrogel water suction sufficiently swelling
Water imbibition, water-retaining property.Due to its superelevation water content, porous structure and soft uniform quality, hydrogel is than other any conjunctions
At biomaterial Geng Neng natural imitation biological tissue, be a kind of common tissue engineering bracket material.
Wherein, it is commonly used for since fibroin albumen has the properties such as excellent mechanical performances, biocompatibility and resistance to enzymic degradation
Tissue engineering bracket material, and fibroin albumen has diversified plastic mode, and this is established for the building of organizational project complex
Basis is determined.Fibroin albumen can be interacted by hydrogen bond, hydrophilic and hydrophobic, electrostatic and shearing force etc., so that between strand
It interacts and induces its crystallization, cause mutually to wind between macromolecular chain, gather, formation protein microsphere micella is simultaneously further
Physical crosslinking forms hydrogel.In addition to this, due to containing a large amount of active group on its side chain, it can be modified by sulphation and hand over
The hydrogel material of chemical covalent crosslinking is prepared in connection.
Hyaluronic acid (HyaluronicAcid, the HA) constituent important as one kind of natural extracellular matrix, by
In its stronger water absorbing properties and it is rich in can modification activities group and be usually used in improving the whole hydrophily of hydrogel
And toughness.There are a large amount of carboxyl and hydroxyls on HA macromolecular chain, it may be convenient to which the HA for being modified to various functional groups spreads out
Biology, molecular weight distribution is very extensive, and from 1-10000kDa, and according to the difference of molecular weight, HA plays different in human body
Effect, the HA of high molecular weight are often applied to the junction of elastic fibrous tissue, play a buffering connection function, and low molecule HA can be with
Play induced intracellular signal transmitting.Due to having these excellent properties, HA and its derivative are by extensive organizational project
Field.
Currently, people have carried out a large amount of research work using two kinds of base stocks of fibroin albumen and hyaluronic acid, such as
It is prepared for a kind of fibroin albumen compatible with good biological-hyaluronic acid composite hydrogel using ultrasonic plastic technology, is studied
The secondary structure and biocompatibility of the composite hydrogel, the introducing of high spot reviews HA is for improving swelling behavior characteristic
Significance, it was confirmed that when the content of HA be less than 40% when, composite hydrogel system have stable swellability, without change
Stable aquogel system can be obtained by learning crosslinking, and take the lead in confirming when the HA content in composite hydrogel system is in 26-
When between 35%, the formation of fibroin albumen beta sheet structure can be significantly induced, this is conducive to the power for enhancing composite hydrogel system
Learn performance.Although research and utilization HA improves the toughness of hydrogel entirety, this pure physical crosslinking to a certain extent
Application of the mechanical strength of hydrogel in terms of those load-bearing soft tissues is still slightly inadequate, and simple compound HA not with SF
An entirety is formed, hydrogel crosslink density is finally will lead to and is difficult to control.
To solve the above-mentioned problems, in recent years, there is researcher to modify HA using tyrasamine, introduce phenol on the skeleton of HA
Group utilizes horseradish peroxidase and H2O2The controllable hydrogel material of mechanical strength is prepared in catalyst system, due to fibroin egg
There is also tyrosine on white, and the crosslinking of three kinds of different modes can then occur under this catalyst system, first is that fibroin albumen
With the crosslinking of the m-Tyrosine of fibroin albumen, second is that the crosslinking between HA-Tyr and fibroin albumen, third is that tyrasamine between HA-Tyr
Crosslinking, this mode is abundant to combine HA and the respective advantage of fibroin albumen, and one side HA can improve pure silk fibroin water
The problems such as swellbility existing for gel is low, and brittleness is big, enhances its viscoplasticity and hydrophily, and another aspect fibroin albumen can enhance pure
The mechanical strength of HA-Tyr hydrogel, it is final to realize that superiority and inferiority is complementary.Their result of study shows can by the content for increasing HA
Shorten gelation time and can increase degradation rate, and over time, these variations can cause hydrogel in mechanics, protect
Aqueous and crystallization process variation.But the preparation of the method hydrogel is mediated by pure chemistry cross-linking reaction, and still having needs
Want the defect of longer gelation time (20min) and lower early stage elasticity modulus (10kPa).
Summary of the invention
For defect present in existing pure physics and pure chemistry crosslinking technological, the present invention is to improve organizational project gel material
For the purpose of the physicochemical property and biocompatibility of material, one kind is disclosed based on physical-chemical double cross connection and prepares fibroin albumen-tyrasamine
The method of modified hyaluronic acid hydrogel material is passed through using two kinds of base stocks of fibroin albumen and tyrasamine modified hyaluronic acid
Chemical crosslinking and the method that combines of physical crosslinking are prepared that have can gel in-situ, excellent biocompatibility and high-strength and high ductility
Fibroin albumen-hyaluronic acid gel.
For achieving the above object, specific the technical solution adopted is as follows:
1, a kind of that fibroin albumen-tyrasamine modified hyaluronic acid hydrogel material side is prepared based on physical-chemical double cross connection
Method comprises the technical steps that:
1) fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution are prepared
It is the horseradish peroxidase solution of 10U/ml to being completely dissolved by solvent compound concentration of phosphate buffer, and marks
It is denoted as HRP solution, is saved at 4 DEG C；It weighs tyrasamine modified hyaluronic acid and is added in HRP solution that concussion is fast instant at room temperature
Solution, saves at 4 DEG C, and silk fibroin protein solution is then added and is softly mixed, is carried out stirring at low speed mixing with rotation blending instrument
Uniformly, fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution are obtained；
2) fibroin albumen-tyrasamine modified hyaluronic acid hydrogel is prepared
Hydrogenperoxide steam generator is added into the prepared pre-gathering solutions of step 1), pre-polymer solution occurs to hand over reaction, entirely
Reaction rotation blending instrument on carry out, keep reaction -40 minutes 30 minutes, to after reaction by reaction system be placed in 37 DEG C -
Stand -5 minutes 3 minutes in 45 DEG C of insulating boxs, then by after cross-linking reaction product taking-up be placed in centrifuge tube or 24 orifice plates into
Row ultrasonic treatment, amplitude of ultrasonic are set as 40%-50%, and ultrasonic time is -20 seconds 16 seconds, in 37 DEG C -45 DEG C after ultrasound
- 40 minutes 30 minutes are stood to guarantee fibroin albumen sufficient crystallising under the conditions of temperature, obtain hydrogel material.It is rotated in this step
The use of blending instrument can promote the phenylol on phenol and fibroin albumen on the tyrasamine modified hyaluronic acid in pre-polymer solution
Group sufficiently crosslinks reaction, and the ultrasonic treatment in this step can be accelerated to induce the formation of fibroin albumen beta sheet structure.
Further, the step 1) fibroin albumen uses the process for separating and purifying of successively degumming, dissolution, dialysis, concentration.
Further, the step 1) process for separating and purifying is referring to specification [0022] section-in 108653810 A of CN
[0031] section disclosed method.
Further, step 1) the horseradish peroxidase solution preparation method are as follows: weigh a certain amount of horseradish peroxidase
Powder is placed in 50ml centrifuge tube, and is dissolved at normal temperature with phosphate buffer, and the content of horseradish peroxidase is controlled
For 10U/ml, it is placed on 4 DEG C of refrigerators after being completely dissolved and saves；
Further, fibroin albumen content is 64mg/ml in the step 1) pre-polymer solution, and tyrasamine modified hyaluronic acid contains
Amount is 1~3mg/ml, and horseradish peroxidase content is 2U/ml, and the hydrogen peroxide being added in step 2) into pre-polymer solution contains
Amount is 20mmol/L.
The beneficial effects of the invention are that:
The present invention utilizes two kinds of base stocks of fibroin albumen and tyrasamine modified hyaluronic acid, is handed over using chemical crosslinking and physics
Join the method that combines be prepared with can gel in-situ, excellent biocompatibility and high-strength and high ductility fibroin albumen-it is transparent
Matter acid hydrogel.By the optimization of the technical program, it may be implemented to shorten fibroin albumen crystallization fringe time and can accelerate pre-
Poly solution gelation increases the rigidity of hydrogel entirety, while being chemically crosslinked makes fibroin albumen and hyaluronic acid be cross-linked with each other shape
At a kind of network structure, the toughness for improving hydrogel is realized.The technical program designs tissue engineering bracket material and prepares tool
There is reference significance.
Figure of description
Fig. 1 is the hydrogel pictorial diagram being prepared by embodiment 1；
Fig. 2 is the mechanical property comparison diagram for the hydrogel being prepared by different crosslinking methods；
SEM picture of the position Fig. 3 by the hydrogel that embodiment 1 is prepared after freeze-dried.
Specific embodiment
Technical solution of the present invention is described further below in conjunction with Figure of description and specific embodiment:
Fibroin albumen used in following embodiment is referring to specification [0022] section-[0031] section in 108653810 A of CN
Prepared by disclosed method.
Tyrasamine modified hyaluronic acid used in following embodiment the preparation method comprises the following steps:
1g hyaluronic acid is dissolved in 100mL deionized water, 202mg tyrasamine hydrochloric acid is further added after being completely dissolved
Salt then successively adds 290mg n-hydroxysuccinimide (NHS) and 479mg1- (3- dimethylamino-propyl) -3- ethyl carbon
Diimmonium salt hydrochlorate (EDCHCl) activates the carboxyl of HA and starts entire reaction, uses 0.1mol/L dilute hydrochloric acid until completely dissolved
The pH value of reaction solution is alternately adjusted with the sodium hydroxide of 0.1mol/L to 4.7, and is allowed to reaction overnight, is adjusted after reaction anti-
It answers the pH value of liquid to 7, is then transferred to reaction solution in the bag filter that molecular cut off is 1000Da, in the chlorination of 0.1mol/L
It dialyses two days in sodium solution, in ethyl alcohol: dialysing 1 day in deionized water=1:3 mixed solution, dialyse one in deionized water
It, finally dispenses solution into big ware, is put into -80 DEG C of refrigerator, then carries out vacuum freeze drying, obtains spongiform
HA-Tyr sample is with spare.
One kind disclosed in Examples 1 to 3 is based on physical-chemical double cross connection and prepares fibroin albumen-tyrasamine modified hyaluronic acid
The method of hydrogel material, according to following processing step:
1) fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution are prepared
It is the horseradish peroxidase solution of 10U/ml to being completely dissolved by solvent compound concentration of phosphate buffer, and marks
It is denoted as HRP solution, is saved at 4 DEG C；It weighs tyrasamine modified hyaluronic acid and is added in HRP solution that concussion is fast instant at room temperature
Solution, saves at 4 DEG C, and silk fibroin protein solution is then added and is softly mixed, is carried out stirring at low speed mixing with rotation blending instrument
Uniformly, fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution are obtained；
2) fibroin albumen-tyrasamine modified hyaluronic acid hydrogel is prepared
Hydrogenperoxide steam generator is added into the prepared pre-gathering solutions of step 1), pre-polymer solution occurs to hand over reaction, entirely
Reaction carries out on rotation blending instrument, keeps reaction 30min, is placed in reaction system to after reaction quiet in 37 DEG C of insulating boxs
It sets 3 minutes, then the product taking-up after cross-linking reaction is placed in centrifuge tube or 24 orifice plates and is ultrasonically treated, amplitude of ultrasonic
It is set as 40%, ultrasonic time 16s, stands 40 minutes under the conditions of 37 DEG C of temperature after ultrasound to guarantee that fibroin albumen is abundant
Crystallization, obtains hydrogel material.
Embodiment 1
Fibroin albumen content is 64mg/ml, the modified hyalomitome of tyrasamine in the step 1) pre-polymer solution in the present embodiment
Acid content is 1mg/ml, and horseradish peroxidase content is 2U/ml, and the hydrogen peroxide being added in step 2) into pre-polymer solution contains
Amount is 20mmol/L, and the hydrogel being prepared is labeled as SH-T1.
Embodiment 2
Fibroin albumen content is 64mg/ml, the modified hyalomitome of tyrasamine in the step 1) pre-polymer solution in the present embodiment
Acid content is 2mg/ml, and horseradish peroxidase content is 2U/ml, and the hydrogen peroxide being added in step 2) into pre-polymer solution contains
Amount is 20mmol/L, and the hydrogel being prepared is labeled as SH-T2.
Embodiment 3
Fibroin albumen content is 64mg/ml, the modified hyalomitome of tyrasamine in the step 1) pre-polymer solution in the present embodiment
Acid content is 3mg/ml, and horseradish peroxidase content is 2U/ml, and the hydrogen peroxide being added in step 2) into pre-polymer solution contains
Amount is 20mmol/L, and the hydrogel being prepared is labeled as SH-T3.
As shown in FIG. 1, FIG. 1 is the hydrogel pictorial diagrams being prepared by embodiment 1.There is Fig. 1 can be seen that, is prepared
Hydrogel surface it is smooth.
The hydrogel that further embodiment 1 is prepared carries out Mechanics Performance Testing, and hands over the pure physics of the prior art
The hydrogel that connection and pure chemistry cross-linking method obtain is compared, and is intuitively recorded in Fig. 2, and A1, A2, A3 distinguish table in Fig. 2
Show it is pure be physical crosslinking obtained hydrogel by before pressing, after pressing, the picture of final form；B1, B2, B3 respectively indicate purifying
Learn the obtained hydrogel of crosslinking by before pressing, after pressing, the picture of final form；C1, C2, C3 respectively indicate physical chemistry friendship
Join obtained hydrogel by before pressing, after pressing, the picture of final form；Can reflecting physical crosslinking by Fig. 2, there are larger
Brittleness, and be chemically crosslinked there are stronger toughness, advantage that both joint crosslinking combines.
After the hydrogel that Examples 1 to 3 is obtained is freeze-dried, the SEM being irradiated under different multiples schemes
Piece, thus figure can be seen that equally distributed, open cavernous structure is presented in the hydrogel that Examples 1 to 3 is prepared.By this water
Gel is very beneficial for the matter transportation of cell as tissue engineering bracket material.
Can to sum up it illustrate, the present invention utilizes two kinds of base stocks of fibroin albumen and tyrasamine modified hyaluronic acid, using chemistry
Crosslinking and the method that combines of physical crosslinking be prepared with can gel in-situ, excellent biocompatibility and high-strength and high ductility silk
Fibroin-hyaluronic acid gel.
Finally, it is stated that above, the embodiment of the present invention is explained in detail, but of the invention and unlimited
In above embodiment, within the knowledge of a person skilled in the art, ancestor of the present invention can also not departed from
Various changes can be made under the premise of purport.
Claims (5)
1. a kind of prepare fibroin albumen-tyrasamine modified hyaluronic acid hydrogel material method based on physical-chemical double cross connection,
It is characterized in that, comprises the technical steps that:
1) fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution are prepared
It is the horseradish peroxidase solution of 10U/ml to being completely dissolved by solvent compound concentration of phosphate buffer, and is labeled as
HRP solution saves at 4 DEG C；It weighs tyrasamine modified hyaluronic acid and the quickly dissolution of concussion at room temperature is added in HRP solution, in 4
It is saved at DEG C, silk fibroin protein solution is then added and is softly mixed, stir at low speed with rotation blending instrument uniformly mixed, obtains
Fibroin albumen, tyrasamine modified hyaluronic acid pre-polymer solution；
2) fibroin albumen-tyrasamine modified hyaluronic acid hydrogel is prepared
Hydrogenperoxide steam generator is added into the prepared pre-gathering solutions of step 1), pre-polymer solution occurs to hand over reaction, entire to react
It is carried out on rotation blending instrument, reaction -40 minutes 30 minutes is kept, to which reaction system is placed in 37 DEG C -45 DEG C after reaction
- 5 minutes 3 minutes are stood in insulating box, then the product taking-up after cross-linking reaction is placed in centrifuge tube or 24 orifice plates and is surpassed
Sonication, amplitude of ultrasonic are set as 40%-50%, and ultrasonic time is -20 seconds 16 seconds, in 37 DEG C of -45 DEG C of temperature after ultrasound
Under the conditions of stand -40 minutes 30 minutes to guarantee fibroin albumen sufficient crystallising, obtain hydrogel material.
2. a kind of according to claim 1 prepare fibroin albumen-tyrasamine modified hyaluronic acid water-setting based on physical-chemical crosslinking
The method of glue material, which is characterized in that the step 1) fibroin albumen uses the separation of successively degumming, dissolution, dialysis, concentration
Purifying technique.
3. a kind of according to claim 2 prepare fibroin albumen-tyrasamine modified hyaluronic acid water-setting based on physical-chemical crosslinking
The method of glue material, which is characterized in that the step 1) process for separating and purifying is referring to specification [0022] in CN108653810A
Section-[0031] section disclosed method.
4. a kind of according to claim 1 prepare fibroin albumen-tyrasamine modified hyaluronic acid water-setting based on physical-chemical crosslinking
The method of glue material, which is characterized in that step 1) the horseradish peroxidase solution preparation method are as follows: weigh a certain amount of horseradish
Peroxidase powder is placed in 50ml centrifuge tube, and is dissolved at normal temperature with phosphate buffer, and horseradish peroxidating is controlled
The content of enzyme is 10U/ml, and 4 DEG C of refrigerators are placed on after being completely dissolved and are saved.
5. a kind of according to claim 1 prepare fibroin albumen-tyrasamine modified hyaluronic acid water-setting based on physical-chemical crosslinking
The method of glue material, which is characterized in that fibroin albumen content is 64mg/ml in the step 1) pre-polymer solution, and tyrasamine is modified
Hyaluronic acid contents are 1~3mg/ml, and horseradish peroxidase content is 2U/ml, are added in step 2) into pre-polymer solution
Content of hydrogen peroxide is 20mmol/L.
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| CN201910534888.XA CN110172163B (en) | 2019-06-20 | 2019-06-20 | Method for preparing silk fibroin-tyramine modified hyaluronic acid hydrogel material based on physical-chemical double crosslinking |
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| CN110527116A (en) * | 2019-09-17 | 2019-12-03 | 江南大学 | A kind of method that enzyme process prepares the compound outer compress material of fibroin/hyaluronic acid |
| CN110591168A (en) * | 2019-09-17 | 2019-12-20 | 江南大学 | Method for preparing hyaluronic acid-based conductive film material by enzyme method |
| CN114404797A (en) * | 2022-01-25 | 2022-04-29 | 重庆科技学院 | Self-curling double-layer hydrogel microneedle patch and preparation method thereof |
| CN114601958A (en) * | 2022-03-25 | 2022-06-10 | 武竞衡 | Hyaluronic acid/silk fibroin double-crosslinking injectable hydrogel and preparation method thereof |
| CN115260531A (en) * | 2022-08-04 | 2022-11-01 | 重庆科技学院 | Preparation method of self-crimpable double-layer hydrogel sheet |
| CN116870241A (en) * | 2023-08-03 | 2023-10-13 | 海南大学 | In-situ formed double-network hydrogel dressing and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110527116A (en) * | 2019-09-17 | 2019-12-03 | 江南大学 | A kind of method that enzyme process prepares the compound outer compress material of fibroin/hyaluronic acid |
| CN110591168A (en) * | 2019-09-17 | 2019-12-20 | 江南大学 | Method for preparing hyaluronic acid-based conductive film material by enzyme method |
| CN114404797A (en) * | 2022-01-25 | 2022-04-29 | 重庆科技学院 | Self-curling double-layer hydrogel microneedle patch and preparation method thereof |
| CN114601958A (en) * | 2022-03-25 | 2022-06-10 | 武竞衡 | Hyaluronic acid/silk fibroin double-crosslinking injectable hydrogel and preparation method thereof |
| CN115260531A (en) * | 2022-08-04 | 2022-11-01 | 重庆科技学院 | Preparation method of self-crimpable double-layer hydrogel sheet |
| CN115260531B (en) * | 2022-08-04 | 2024-03-22 | 重庆科技学院 | Preparation method of self-curling double-layer hydrogel sheet |
| CN116870241A (en) * | 2023-08-03 | 2023-10-13 | 海南大学 | In-situ formed double-network hydrogel dressing and preparation method and application thereof |
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