CN109517118A - A kind of high-strength degradable hydrogel and preparation method thereof - Google Patents
A kind of high-strength degradable hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN109517118A CN109517118A CN201710841822.6A CN201710841822A CN109517118A CN 109517118 A CN109517118 A CN 109517118A CN 201710841822 A CN201710841822 A CN 201710841822A CN 109517118 A CN109517118 A CN 109517118A
- Authority
- CN
- China
- Prior art keywords
- initiator
- hydrogel
- gelatin
- strength
- glycine
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/145—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
Abstract
The present invention discloses a kind of high-strength degradable hydrogel and preparation method thereof; poly- N- acryloyl glycine is crosslinked using methacrylation gelatin; the degradability of methacrylation gelatin and the high intensity of poly- N- acryloyl glycine hydrogel are combined, which has high strength characteristics and degradability simultaneously.
Description
Technical field
The invention belongs to technical field of hydrogel, more particularly, are related to a kind of system of high-strength degradable hydrogel
It is standby, specially a kind of preparation of N- acryloyl glycine-methacrylation gelatin (P (ACG/GelMA)) hydrogel, the water-setting
Glue is crosslinked poly- N- acryloyl glycine using methacrylation gelatin, combine methacrylation gelatin degradability and
The high intensity of poly- N- acryloyl glycine hydrogel, the gel have high strength characteristics and degradability simultaneously.
Background technique
It is past during the decade, it is high-strength to have benefited from such as double-network hydrogel, Nanometer composite hydrogel, supramolecular hydrogel
The fast development of aquogel system, hydrogel be not limited only to be a kind of " soft and wet " material.Simultaneously as high-strength water-setting
Glue still possesses hydrogel high-moisture characteristic, that is to say, that high intensity hydrogel it is identical as conventional hydrogels can in drug and
Cell provides beneficial rich water environment when transmitting, and it is certain that this possesses application of the high intensity hydrogel in terms of organizational project still
Advantage.(Gkioni,K.；Leeuwenburgh,S.C.G.；Douglas,T.E.L.；Mikos,A.G.；Jansen,
J.A.Mineralization of hydrogels for bone regeneration.Tissue Eng.,Part B,
2010,16,577-585.) moreover, due to deepening continuously to high-strength hydrogel research, hydrogel is in hard tissue repair side
The application in face has been carried out.(Xu,B.；Zheng,P.；Gao,F.；Wang,W.；Zhang,H.；Zhang,X.；Feng,X.；
Liu.W.A mineralized high strength and tough hydrogel for skull bone
Regeneration.Adv.Funct.Mater., 2017,27,1604327.) however, high-strength hydrogel is generally applied to prop up
Timbering material, non-biodegradable significantly limit the validity of its cell or drug delivery.Therefore, non-biodegradable is at certain
Application of the high-strength hydrogel in terms of organizational project is limited in degree.
Not long ago, we are by synthesizing and polymerizeing the monomer N- acryloyl for having an amino and a carboxyl on a kind of side chain
Glycine (ACG) is prepared for poly- N- acryloyl glycine (PACG) supramolecular hydrogel.(Gao,F.；Zhang,Y.；Li,Y.；
Xu,B.；Cao,Z.；Liu,W.Sea cucumber-inspired autolytic hydrogels exhibiting
tunable high mechanical performances,repairability,and reusability.ACS
Appl.Mater.Interfaces, 2016,8,8956-8966.) since there are carboxyls in PACG hydrogel at various ph values
Hydrogen bond is dynamically formed and destructive process, and PACG hydrogel can form stable and high-strength hydrogel network in acid condition,
It can slowly dissociate under neutral or basic conditions.However, since its degradability and high epistasis can not be realized under identical conditions, because
This strictly speaking, PACG hydrogel is not high-strength degradable hydrogel truly.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high-strength degradable hydrogel and its preparations
Method, the high-strength degradable hydrogel based on N- acryloyl glycine, specially N- acryloyl glycine-methacryl
Change gelatin (P (ACG/GelMA)) hydrogel, which possesses high strength characteristics and degradability simultaneously, that is, utilizes methacryl
High-strength and degradable hydrogel can be formed by changing gelatin (GelMA) crosslinking N- acryloyl glycine (ACG).Simple ACG polymer
It is easy in water and/or alkaline condition is dissociated or degraded, but the hydrogel after the two copolymerization in the present invention is in alkali
Property under the conditions of (close under the pH value condition of human body vivo environment, such as 7-8) be stabilized and keep hydrogel shape, show
Reach the stretching and compressive strength of MPa, and shows to continue slowly to degrade.
Technical purpose of the invention is achieved by following technical proposals:
A kind of high-strength degradable hydrogel and preparation method thereof, by monomer N- acryloyl glycine, methacrylation
Gelatin and initiator are evenly dispersed in water, then cause the sweet ammonia of N- acryloyl by the effect of initiator under anaerobic
Unsaturated carbon carbon bond on acid and methacrylation gelatin carries out Raolical polymerizable, to realize the sweet ammonia of monomer N- acryloyl
The copolymerization of acid and methacrylation gelatin forms the hydrogel with high strength characteristics and degradability.
In the above-mentioned technical solutions, the mass ratio of N- acryloyl glycine and methacrylation gelatin is (10-15):
1, preferably (10-12): 1.
In the above-mentioned technical solutions, solid content is 20-30%, preferably 20-25%, and solid content is two kinds of monomer N- propylene
The quality sum of acyl glycine and methacrylation gelatin/(quality sum of two kinds of monomers and water).
In the above-mentioned technical solutions, N- acryloyl glycine (ACG) is to contain an amino and a carboxylic in a kind of side group
On the one hand the monomer of base can form hydrogen bond after polymerisation, on the other hand can form ionomer network, first under calcium ion effect
The acrylated gelatin of base (GelMA) is a kind of monomer with methylacryloyl, and chemically cross-linkable polymer stablizes polymer
Network.Due to the clostridiopetidase A degradability of gelatin and the polymerizability of methylacryloyl, methacrylation gelatin (GelMA)
Polymer can be chemically crosslinked under the action of initiator can decline solution in collagen enzyme effect simultaneously.
In the preparation method of above-mentioned hydrogel, initiator amount is 1%-the 5% of the sum of two kinds of monomer masses, preferably 1-
3%, such as azodiisobutyronitrile (ABIN), benzoyl peroxide (BPO) thermal initiator can be selected, such as 1- [4- (2- also can be selected
Hydroxy ethoxy)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl ethyl ketones (Irgacure 2959), methyl vinyl ketone, styrax
Equal photoinitiators.If but should be noted that and select thermal initiator, to avoid inhibition, it is necessary to be passed through in the reaction system
Inert gas makes initiation reaction system to remove oxygen, while to enable initiator to generate enough free radicals for a long time
Raolical polymerizable persistently occurs, it is necessary to reaction system is heated on the initiation temperature of initiator used and keep 1h with
Upper or longer (1-5h) time；If selecting photoinitiator, transparent closed reaction vessel must be selected, in ultraviolet light
Under conditions of cause free radical polymerization, due to light-initiated efficiency be higher than heat cause, because of the activity and dosage of the initiator according to selected by
When adjusting irradiation time, irradiation time be can be selected 20 minutes or longer (30min-1h).
Compared with prior art, a kind of high-strength degradable hydrogel provided by the invention is with N- acryloyl glycine and first
The acrylated gelatin of base is raw material, is copolymerized and is made under initiator existence condition.Since there are N- acryloyl is sweet in gel network
The physical crosslinking effect and the chemical crosslinking of methacrylation gelatin that propylhomoserin intermolecular hydrogen bonding is formed act on, this hydrogel tool
There is good mechanical property.Simultaneously as methacrylation gelatin can degrade under the action of clostridiopetidase A, and poly- N- acryloyl
Glycine can dissociate under neutral or basic conditions, and this hydrogel can degrade in collagenase solution.
Detailed description of the invention
Fig. 1 is the infrared spectrum of P of the invention (ACG/GelMA) hydrogel.
Fig. 2 is the equilibrium moisture content of P of the invention (ACG/GelMA) hydrogel at different conditions.
Fig. 3 is the stereoscan photograph of P of the invention (ACG/GelMA) hydrogel at different conditions.
Fig. 4 is the degradation process test curve figure of P of the invention (ACG/GelMA) hydrogel.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.In the embodiment of the present invention using drug and
Instrument is commercially available conventional medication and equipment, N- acryloyl glycine (ACG) be using acryloyl chloride and glycine as raw material according to
It is prepared according to bibliography, which is not described herein again, can particular reference Gao, F.；Zhang,Y.；Li,Y.；Xu,B.；Cao,Z.；
Liu,W.Sea cucumber-inspired autolytic hydrogels exhibiting tunable high
mechanical performances,repairability,and reusability.ACS
Appl.Mater.Interfaces,2016,8,8956-8966.Methacrylation gelatin is with methacrylic anhydride and gelatin
It is prepared for raw material, according to bibliography (Resmi, R.；Unnikrishnan,S.；Krishnan,L.K.；Krishnan,
V.K.Synthesis and characterization of silver nanoparticle incorporated
gelatin-hydroxypropyl methacrylate hydrogels for wound dressing
Applications.J.Appl.Polym.Sci.2017,134,44529) preparation, it is obtained by carrying out chemical modification to gelatin
Methacrylation gelatin (GelMA).
By monomer N- acryloyl glycine (230.8mg), methacrylation gelatin (19.2mg) is added to 4ml centrifuge tube
In, 2.5 μ l photoinitiator IRGACURE-1173 (2- hydroxyls are added after being completely dissolved in 40 DEG C of water-baths with the deionized water of 750 μ l
Base-2- methyl-1-phenyl-1- acetone, 98%, Sigma).It then, will be containing in the solvent of monomer and initiator injection mold
(internal diameter 1mm, outer diameter 1.8mm), the irradiation in ultra-violet curing case (XL-1000UV, Spectronics Corporation)
40min sufficiently causes free radical polymerization.After the completion of polymerization, with deionized water repeated flushing to go after gel is removed from the molds
Except wherein unreacted monomer and impurity.Obtained hydrogel is placed in deionized water until swelling equilibrium.
Using Fourier Transform Infrared Spectrometer (FTIR, Spectrum 100FTIR Spectrometer,
PerkinElmer Inc., USA) dry P (ACG/GelMA) hydrogel powders of measurement.1542cm-1、1647cm-1With
1730cm-1The characteristic peak at place be respectively in poly- N- acryloyl glycine the N-H bending vibration characteristic absorption peak of amino and amino and
C=O stretching vibration characteristic absorption peak in carboxyl, is detailed in Figure of description 1.
To measure swelling situation of the above-mentioned hydrogel in acid, alkalinity, PBS and ionic calcium soln, by above-mentioned water-setting
Glue immerse respectively acidity (water) solution of pH=3, alkalinity (water) solution of pH=8, pH=7.4 PBS (water) solution and
Until swelling equilibrium, measures the equilibrium moisture content of hydrogel, wherein pH value of solution is by hydrogen chloride water in the calcium chloride water of 0.5M
Solution and sodium hydrate aqueous solution are adjusted.The moisture for being up to the hydrogel surface of swelling equilibrium sucks, and weighing obtains hydrogel
Weight in wet base (Wwet).Then, the dry weight (W of measurement hydrogel after hydrogel being dried in 65 DEG C of baking ovens 24 hours or moredry).Most
Eventually, the equilibrium moisture content (EWC) of hydrogel is calculate by the following formula:
By data as it can be seen that hydrogel can maintain shape under the conditions of pH=8 is below, it is detailed in Figure of description 2.
It is lyophilized, utilizes after P (ACG/GelMA) hydrogel of above-mentioned swelling equilibrium at different conditions is quenched in liquefied ammonia
Field emission scanning electron microscope (FE-SEM, s4800, Hitachi Ltd., Japan) observes gel surface pattern.
It can be seen that the size and bore hole size of hydrogel rise as pH value rises, it is detailed in Figure of description 3.
The size of sample for compression performance test is diameter 4mm, and high 6mm, compression speed is 10mm min-1.For
The size of the sample of tensile property test is long 10mm, wide 2mm, thickness 0.5mm, and rate of extension is 50mm min-1.Test result
Show that hydrogel shows good mechanical property, be detailed in shown in following table, the tensile strength of composite hydrogel is after tested
0.75-0.8MPa, compressive strength are 4.8-5.6MPa.
The hydrogel that weighing is lyophilized in advance is immersed in 4ml PBS solution (pH value 7.4), is added thereto at 37 DEG C of constant temperature
Entering 60 μ l concentration is 1mg ml-1Collagen enzyme aqueous solution, preparation the bibliography Liu, Y. of collagen enzyme aqueous solution；Yang,J.；
Zhang,P.；Liu,C.；Wang,W.；Liu,W.ZnO quantum dotsembedded collagen/polyanion
composite hydrogels with integrated functions of degradation tracking/
inhibition and gene delivery.J.Mater.Chem.,2012,22,512-519.Then taken in certain time point
Hydrogel out is lyophilized and measures its weight.The residual mass percentage of hydrogel is by Wt/Wo× 100% calculates, wherein WtIt is each
Time point is the quality of hydrogel, WoFor the initial weight of hydrogel.It can be seen that hydrogel is slowly degraded in the solution, degradation process
Continue 6 weeks, is detailed in Figure of description 4.
The hydrogel after two kinds of monomer copolymerization is under alkaline condition (close to the pH value of human body vivo environment in the present invention
Under the conditions of, such as 7-8) it is stabilized and keeps hydrogel shape, the stretching and compressive strength of MPa are exhibited up to, and show
Continue slow degradation property, i.e., hydrogel of the invention is preparing the application in biomaterial.
The technological parameter that content is recorded according to the present invention carries out the adjustment of preparation method, and P (ACG/GelMA) water can be achieved
The preparation of gel, and show the performance almost the same with embodiment.Illustrative description is done to the present invention above, it should say
It is bright, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art
The equivalent replacement of creative work can not be spent to each fall within protection scope of the present invention.
Claims (10)
1. a kind of high-strength degradable hydrogel, which is characterized in that by monomer N- acryloyl glycine, methacrylation gelatin
And initiator is evenly dispersed in water, then under anaerobic by the effect of initiator cause N- acryloyl glycine and
Unsaturated carbon carbon bond on methacrylation gelatin carries out Raolical polymerizable, with realize monomer N- acryloyl glycine and
The copolymerization of methacrylation gelatin, hydrogel are stabilized and keep hydrogel shape, hydrogel under the conditions of pH is 7-8
Tensile strength be 0.75-0.8MPa, compressive strength is 4.8-5.6MPa, and shows the performance for continuing slowly to degrade.
2. a kind of high-strength degradable hydrogel according to claim 1, which is characterized in that N- acryloyl glycine and first
The mass ratio of the acrylated gelatin of base is (10-15): 1, preferably (10-12): 1.
3. a kind of high-strength degradable hydrogel according to claim 1, which is characterized in that solid content is 20-30%,
It is preferred that 20-25%.
4. a kind of high-strength degradable hydrogel according to claim 1, which is characterized in that initiator amount is two kinds of lists
1%-the 5% of the sum of weight, preferably 1-3%, initiator are thermal initiator azodiisobutyronitrile, benzoyl peroxide, are
Avoid inhibition, it is necessary to be passed through inert gas in the reaction system to remove oxygen, while to enable initiator for a long time
Enough free radicals are generated, make initiation reaction system that Raolical polymerizable persistently occur, it is necessary to be heated to reaction system
On the initiation temperature of initiator used and kept for 1h or more or longer (1-5h) time.
5. a kind of high-strength degradable hydrogel according to claim 1, which is characterized in that initiator amount is two kinds of lists
1%-the 5% of the sum of weight, preferably 1-3%, initiator be 1- [4- (2- hydroxy ethoxy)-phenylene]-2- hydroxyl-2 ',
2 '-dimethyl ethyl ketones, methyl vinyl ketone, styrax select transparent closed reaction vessel, under conditions of ultraviolet light
Cause free radical polymerization, cause since light-initiated efficiency is higher than heat, because of activity and dosage the adjustment irradiation of the initiator according to selected by
When the time, irradiation time be can be selected 20 minutes or longer (30min-1h).
6. a kind of preparation method of high-strength degradable hydrogel, which is characterized in that carry out as steps described below: by monomer N- third
Alkene acyl glycine, methacrylation gelatin and initiator are evenly dispersed in water, then pass through initiation under anaerobic
It is anti-that the effect of agent causes the unsaturated carbon carbon bond progress free radical polymerization on N- acryloyl glycine and methacrylation gelatin
It answers, to realize the copolymerization of monomer N- acryloyl glycine and methacrylation gelatin；N- acryloyl glycine and metering system
The mass ratio of acidylated gelatin is (10-15): 1, solid content is 20-30%, and initiator amount is the sum of two kinds of monomer masses
1% -5%.
7. a kind of preparation method of high-strength degradable hydrogel according to claim 7, which is characterized in that N- acryloyl
The mass ratio of glycine and methacrylation gelatin is (10-12): 1.
8. a kind of preparation method of high-strength degradable hydrogel according to claim 7, which is characterized in that solid content is
20-25%.
9. a kind of preparation method of high-strength degradable hydrogel according to claim 7, which is characterized in that initiator is used
Amount is 1-the 3% of the sum of two kinds of monomer masses；Initiator is azodiisobutyronitrile, benzoyl peroxide, 1- [4- (2- hydroxyl ethoxy
Base)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl ethyl ketones, methyl vinyl ketone or styrax；If selecting thermal initiator, it is
Avoid inhibition, it is necessary to be passed through inert gas in the reaction system to remove oxygen, while to enable initiator for a long time
Enough free radicals are generated, make initiation reaction system that Raolical polymerizable persistently occur, it is necessary to be heated to reaction system
On the initiation temperature of initiator used and kept for 1h or more or longer (1-5h) time；If selecting photoinitiator, select
Transparent closed reaction vessel, causes free radical polymerization under conditions of ultraviolet light, since light-initiated efficiency is drawn higher than heat
Hair, because the initiator according to selected by activity and dosage adjustment irradiation time when, optional 20 minutes of irradiation time or longer
(30min-1h)。
10. a kind of high-strength degradable hydrogel as described in claim 1 is preparing the application in biomaterial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841822.6A CN109517118B (en) | 2017-09-18 | 2017-09-18 | High-strength degradable hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841822.6A CN109517118B (en) | 2017-09-18 | 2017-09-18 | High-strength degradable hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109517118A true CN109517118A (en) | 2019-03-26 |
| CN109517118B CN109517118B (en) | 2021-04-30 |
Family
ID=65768103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710841822.6A Expired - Fee Related CN109517118B (en) | 2017-09-18 | 2017-09-18 | High-strength degradable hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109517118B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029055A (en) * | 2019-06-04 | 2020-12-04 | 天津大学 | Supramolecular polymer enhanced biodegradable high-strength gelatin-based hydrogel and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356319A (en) * | 2014-11-03 | 2015-02-18 | 四川大学 | Porous biological material using modified gelatin as crosslinking agent and preparation method of porous biological material |
| CN106397646A (en) * | 2015-08-03 | 2017-02-15 | 天津大学 | High-strength super-molecular hydrogel, preparation method therefor and application of high-strength super-molecular hydrogel |
-
2017
- 2017-09-18 CN CN201710841822.6A patent/CN109517118B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356319A (en) * | 2014-11-03 | 2015-02-18 | 四川大学 | Porous biological material using modified gelatin as crosslinking agent and preparation method of porous biological material |
| CN106397646A (en) * | 2015-08-03 | 2017-02-15 | 天津大学 | High-strength super-molecular hydrogel, preparation method therefor and application of high-strength super-molecular hydrogel |
Non-Patent Citations (7)
| Title |
|---|
| ANDRADA SERAFIM等: "One-pot synthesis of superabsorbent hybrid hydrogels based on methacrylamide gelatin and polyacrylamide. Effortless control of hydrogel properties through composition design", 《NEW J. CHEM.》 * |
| FEI GAO等: "Sea Cucumber-Inspired Autolytic Hydrogels Exhibiting Tunable High Mechanical Performances, Repairability, and Reusability", 《ACS APPL. MATER. INTERFACES》 * |
| HAIRUI SUO等: "Using glucosamine to improve the properties of photocrosslinked gelatin scaffolds", 《JOURNAL OF BIOMATERIALS APPLICATIONS》 * |
| HONGBO WANG等: "A High Strength Self-Healable Antibacterial and Anti-Inflammatory Supramolecular Polymer Hydrogel", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
| 吕志芳等: "聚N-丙烯酰基甘氨酸水凝胶的合成及溶胀性能 ", 《南京工业大学学报(自然科学版)》 * |
| 周超等: "栓塞用水凝胶微球的制备及其理化性质的评价 ", 《北京大学学报(医学版)》 * |
| 王毅虎等: "紫外光共聚交联制备ＧｅｌＭＡ／ＰＥＧＤＡ水凝胶", 《影像科学与光化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029055A (en) * | 2019-06-04 | 2020-12-04 | 天津大学 | Supramolecular polymer enhanced biodegradable high-strength gelatin-based hydrogel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109517118B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106349412B (en) | Application of the supramolecular hydrogel based on acryloyl group glycine amide as self-repair material | |
| CN106397646B (en) | High intensity supramolecular hydrogel and its preparation method and application | |
| CN101161696B (en) | Hydrogel and method for preparing same | |
| CN109206634A (en) | Gelatin-based high intensity hydrogel and preparation method thereof | |
| JP2003500508A (en) | Surface treatment of silicone hydrogel contact lenses containing hydrophilic polymer chains attached to an intermediate carbon coating | |
| CN112111073B (en) | Anti-fatigue full-hydrogel composite material and preparation method and application thereof | |
| CN106947012B (en) | Hydrogel based on methylacryloyl glycine amide and its application as self-repair material | |
| US20230201427A1 (en) | Method for preparing structured hydrogel and method for preparing hydrogel heart valve | |
| CN110885524A (en) | Double-network hydrogel based on polyacryl glycinamide and sodium alginate and preparation method thereof | |
| CN113801262A (en) | High-strength gel and preparation method thereof | |
| CN112029055A (en) | Supramolecular polymer enhanced biodegradable high-strength gelatin-based hydrogel and preparation method and application thereof | |
| CN109575317A (en) | A kind of high intensity hydrogel and preparation method thereof with pH response | |
| CN109517118A (en) | A kind of high-strength degradable hydrogel and preparation method thereof | |
| CN108690309A (en) | High intensity mineralising hydrogel and its application in Bone Defect Repari | |
| CN107778416A (en) | High-strength and high ductility mineralising hydrogel and its preparation method and application | |
| CN109467642B (en) | High-strength temperature-sensitive supramolecular hydrogel capable of being printed in 3D mode and preparation method thereof | |
| CN112430290B (en) | Kappa-carrageenan-based high-strength double-physical crosslinked hydrogel and preparation method thereof | |
| KR102422864B1 (en) | Hydrogels and methods for preparing hydrogels | |
| KR102400716B1 (en) | Hydrogel complex, manufacturing method thereof and transdermal patch using the same | |
| CN110835414A (en) | Biodegradable high-strength hydrogel with pH response, preparation method thereof and application thereof in gastric filler | |
| CN111269353B (en) | Self-repairing material and preparation method thereof | |
| CN109054273B (en) | Double-network hydrogel and preparation method thereof | |
| Pan et al. | Influence of preparation conditions on the properties of keratin-based polymer hydrogel | |
| CN108003288B (en) | Acryloyl glycinamide-1-vinyl-1, 2, 4-triazole high-strength copolymerized hydrogel and preparation method thereof | |
| JP2009256629A (en) | Organic-inorganic composite hydrogel and method for producing the same |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210430 Termination date: 20210918 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |