CN111803707A - Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof - Google Patents
Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN111803707A CN111803707A CN202010503242.8A CN202010503242A CN111803707A CN 111803707 A CN111803707 A CN 111803707A CN 202010503242 A CN202010503242 A CN 202010503242A CN 111803707 A CN111803707 A CN 111803707A
- Authority
- CN
- China
- Prior art keywords
- gelatin
- polysaccharide
- pore
- forming
- hydrogel
- 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.)
- Pending
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
-
- 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
- A61L27/20—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
-
- 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
-
- 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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/06—Flowable or injectable implant compositions
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/02—Dextran; Derivatives thereof
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2405/02—Dextran; Derivatives thereof
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Dermatology (AREA)
- Public Health (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and a preparation method thereof, belonging to the technical field of biomedical high polymer materials. The invention is characterized in that the in-situ pore-forming hydrogel is compounded with a cross-linked gelatin short fiber material, and the hydrogel is enhanced under the condition of not influencing the diffusion of nutrient substances. Preparing a gelatin fiber membrane through electrostatic spinning, performing high-speed shearing treatment to obtain uniformly dispersed short fibers, and preparing cross-linked gelatin short fibers by using glutaraldehyde as a cross-linking agent; introducing the crosslinked gelatin short fiber into an in-situ pore-forming glucan/carboxymethyl chitosan hydrogel system to prepare the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel. The fiber composite in-situ pore-forming injectable hydrogel prepared by the invention has potential application value in the field of tissue engineering.
Description
Technical Field
The invention relates to an injectable hydrogel and a preparation method thereof, in particular to a fiber composite reinforced injectable hydrogel and a preparation method thereof, which are applied to the technical field of medical high polymer materials.
Background
Injectable hydrogel as a special tissue engineering scaffold material has the advantages of minimally invasive injection, easy cell and bioactive molecule entrapment, irregular tissue defect filling and the like, and is widely used for tissue repair and regeneration (Janani Radhakrishnan, Anuradha Subramanian, Swaminathan Sethuraman, Carbohydratepolyelectrolytes, 2017,175, 63-74.). The tissue engineering scaffold material should have a through-going pore structure and high porosity so as to provide sufficient space for the growth, adhesion, proliferation and secretion of extracellular matrix of cells. The introduction of the gelatin microspheres which can be shaped at low temperature and can be dissolved at body temperature can realize the in-situ rapid pore forming in the hydrogel under physiological conditions, and the pore morphology and the pore structure of the hydrogel can be adjusted by changing the size and the dosage of the pore-forming agent (Ting Ting Lau, Chunming Wang, Dong-An Wang, Composites Science and Technology,2010,70(13), 1909-. However, in situ pore formation inside injectable hydrogels can disrupt the continuity and integrity of the hydrogel, leading to deterioration of the mechanical strength of the hydrogel and even structural collapse. Therefore, the mechanical strength of the hydrogel needs to be improved on the premise of ensuring the microporous structure of the hydrogel.
Compounding the hydrogel with the fibrous material can strengthen the hydrogel without affecting the diffusion of nutrients. Electrospinning is one of the common methods for preparing fibers, and fibers of different sizes can be obtained by adjusting electrospinning parameters. Electrospinning, however, can only obtain continuous fibrous membranes, which cannot be directly incorporated into injectable hydrogel systems.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and the preparation method thereof. The fiber composite in-situ pore-forming injectable hydrogel has good application value in tissue engineering.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel comprises the steps of preparing a gelatin fiber membrane through electrostatic spinning, obtaining uniformly dispersed gelatin short fibers after high-speed shearing treatment, and then preparing the gelatin short fibers by using glutaraldehyde as a cross-linking agent; then, preparing temperature response soluble gelatin microspheres as a pore-foaming agent by using polysaccharide as a hydrogel precursor and using an emulsion method; and then, taking gelatin short fibers as a reinforcing agent, and constructing polysaccharide-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction.
As a preferred technical scheme, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by using an emulsion method and used as a pore-forming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction.
As a preferred technical scheme, the preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel comprises the following steps:
a. preparing a gelatin fiber membrane:
dissolving gelatin in a hexafluoroisopropanol solution, preparing a gelatin spinning solution with the concentration of 0.05-0.5 g/mL, sucking the gelatin spinning solution by using an injector, placing the gelatin spinning solution on a propelling table of an electrostatic spinning machine, connecting a high-voltage power supply of 5-15 kV, receiving electrostatic spinning by using tinfoil paper as a receiving device, wherein the receiving distance is 3-9 cm, and the flow rate is 1-10 mL/h, so as to obtain a gelatin fiber membrane; vacuum drying at normal temperature for at least 24h to obtain dry gelatin fiber membrane; the average diameter of the fibers is 500-1000 nm;
b. preparing gelatin short fibers:
b, placing the gelatin fiber membrane obtained in the step a into a beaker filled with ethanol, shearing the gelatin fiber membrane through a high-shear emulsifying machine, and smashing the gelatin fiber membrane to prepare gelatin short fibers; controlling the rotating speed of the emulsifying machine to be 5000-25000 r/min, and controlling the treatment time to be 15-30 min; then centrifuging for at least 20min, removing ethanol, and carrying out vacuum drying at normal temperature for at least 24h to obtain gelatin short fibers with the length of 9-30 mu m;
c. preparation of crosslinked gelatin short fiber:
taking 50mg of the gelatin short fiber obtained in the step b, uniformly dispersing the gelatin short fiber in 5mL of mixed solution of glutaraldehyde and ethanol, stirring at room temperature, carrying out crosslinking reaction for 15-30 min, then carrying out centrifugal treatment on a crosslinking product, washing with absolute ethanol for at least three times, and then drying the cleaned crosslinking product for at least 24h under the conditions of normal temperature and vacuum to obtain the crosslinked gelatin short fiber;
d. uniformly mixing a gelatin microsphere pore-foaming agent with the diameter of 100-400 mu m with a carboxymethyl chitosan precursor solution to obtain a component I; uniformly mixing the crosslinked gelatin fiber obtained in the step c and the oxidized dextran precursor solution to obtain a second component; in the component I, the content of the gelatin microsphere pore-forming agent is not less than 0.03 g/mL; in the second component, the content of the crosslinked gelatin short fiber is 0.01-0.05 g/mL; the molar ratio of aldehyde groups in the oxidized glucan to amino groups in the carboxymethyl chitosan is 1: 1, the total concentration of the oxidized dextran and the carboxymethyl chitosan as a high-molecular precursor is not lower than 3 percent;
e. and d, respectively filling the two solutions of the two components obtained in the step d into two syringes of a double-syringe injector, injecting the two solutions into a mold, forming hydrogel after 30-300 s, and finally placing the hydrogel at a temperature of not higher than 37 ℃ for at least 72h until gelatin microspheres are dissolved out, thereby obtaining the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel.
The method of the invention compounds the in-situ pore-forming hydrogel and the cross-linked gelatin short fiber material, and strengthens the hydrogel under the condition of not influencing the diffusion of nutrient substances. Preparing a gelatin fiber membrane through electrostatic spinning, performing high-speed shearing treatment to obtain uniformly dispersed short fibers, and preparing cross-linked gelatin short fibers by using glutaraldehyde as a cross-linking agent; introducing the crosslinked gelatin short fiber into an in-situ pore-forming glucan/carboxymethyl chitosan hydrogel system to prepare the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel. The fiber composite in-situ pore-forming injectable hydrogel prepared by the invention has potential application value in the field of tissue engineering.
In the step b, the rotation speed of the centrifuge is controlled to be at least 12000r/min for centrifugal treatment.
In the step c, the mass percentage concentration of the glutaraldehyde in the mixed solution of the glutaraldehyde and the ethanol is 0.1-0.5%.
In the step d, the amino content in the carboxymethyl chitosan is not lower than 3.4 mmol/g; the content of aldehyde groups in the oxidized glucan is not less than 4 mmol/g.
The invention discloses polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel, which is prepared by utilizing the preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel.
As a preferred technical scheme, the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel has the storage modulus of 0.5-5 kPa and the porosity of 60-95%.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention respectively takes soluble gelatin microspheres and crosslinked gelatin short fibers as pore-forming agents and reinforcing agents to construct polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel; the hydrogel aims to solve the problem that the mechanical strength of the injectable hydrogel is generally reduced and the structure is collapsed after the microporous structure is formed in situ in the injectable hydrogel;
2. the fiber composite in-situ pore-forming injectable hydrogel has good application value in the field of tissue repair and regeneration;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
Fig. 1 is a schematic flow chart of a method for constructing the fiber composite in-situ pore-forming injectable hydrogel.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) preparing a gelatin fiber membrane:
dissolving gelatin in hexafluoroisopropanol to prepare a gelatin spinning solution with the concentration of 0.1 g/mL; absorbing the spinning solution by using an injector, placing the spinning solution on a propelling table of an electrostatic spinning machine, connecting with an 8kv high-voltage power supply, receiving by using a tin foil paper as a receiving device, wherein the receiving distance is 6cm, the flow rate is 1mL/h, and the drying is carried out in vacuum at normal temperature for 24h to obtain a dry gelatin fiber membrane, and the average diameter of the fiber is 550 nm;
(2) preparing gelatin short fibers:
placing the gelatin fiber membrane in a beaker filled with ethanol, shearing by a high-shear emulsifying machine, crushing the gelatin fiber membrane to prepare gelatin short fibers, wherein the rotating speed of the emulsifying machine is 19000r/min, and the treatment time is 15 min; centrifuging for 10min to remove ethanol, controlling the rotation speed of a centrifuge to be 12000r/min, and vacuum drying at normal temperature for 24h to obtain dry gelatin short fibers with the average length of 17 μm;
(3) preparation of crosslinked gelatin short fiber:
taking 50mg of the gelatin short fiber obtained in the step (2), uniformly dispersing the gelatin short fiber in 5mL of mixed solution of glutaraldehyde and ethanol, wherein the mass percentage concentration of the glutaraldehyde in the mixed solution of the glutaraldehyde and the ethanol is 0.3 wt.%, stirring at room temperature, carrying out crosslinking reaction for 15min, centrifuging the resultant solution, washing with absolute ethyl alcohol for three times, and carrying out vacuum drying at room temperature for 24h to obtain the crosslinked gelatin short fiber;
(4) preparation of hydrogel precursor:
selecting carboxymethyl chitosan with amino content of 3.4mmol/g and oxidized dextran with aldehyde content of 4mmol/g as polymer precursor materials, wherein the molar ratio of aldehyde group to amino group in the polymer precursor is 1: 1, respectively preparing oxidized glucan precursor aqueous solution and carboxymethyl chitosan precursor aqueous solution with corresponding concentrations for later use, wherein the total concentration of the oxidized glucan and the carboxymethyl chitosan as polymer precursor materials is 3%;
(5) preparing gelatin microspheres:
preparing gelatin solution, and preparing pore-foaming agent gelatin microspheres with the diameter of 150-;
(6) mixing the gelatin microspheres obtained in the step (5) with the carboxymethyl chitosan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed first precursor solution as a component one, and mixing the crosslinked gelatin fibers obtained in the step (3) with the oxidized glucan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed second precursor solution as a component two; the content of the gelatin microspheres is 0.03g/mL, and the content of the crosslinked gelatin fibers is 0.01 g/mL;
(7) and (4) respectively filling the two solutions of the components obtained in the step (6) into a double-needle-cylinder injector, injecting the double-needle-cylinder injector into a mold, waiting for 90s to form hydrogel, finally, keeping the hydrogel at 37 ℃ for 72h, and dissolving out gelatin microspheres to obtain the fiber composite in-situ pore-forming hydrogel. The fiber composite in-situ pore-forming hydrogel prepared in the embodiment has the storage modulus of 1.2kPa and the porosity of 83 percent.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) preparing a gelatin fiber membrane:
dissolving gelatin in hexafluoroisopropanol to prepare a gelatin spinning solution with the concentration of 0.1 g/mL; absorbing the spinning solution by using an injector, placing the spinning solution on a propelling table of an electrostatic spinning machine, connecting with an 8kv high-voltage power supply, receiving by using a tin foil paper as a receiving device, wherein the receiving distance is 6cm, the flow rate is 5mL/h, and the drying is carried out in vacuum at normal temperature for 24h to obtain a dry gelatin fiber membrane, and the average diameter of the fiber is 550 nm;
(2) preparing gelatin short fibers:
placing the gelatin fiber membrane in a beaker filled with ethanol, shearing by a high-shear emulsifying machine, crushing the gelatin fiber membrane to prepare gelatin short fibers, wherein the rotating speed of the emulsifying machine is 10000r/min, and the treatment time is 15 min; centrifuging for 10min to remove ethanol, controlling the rotation speed of a centrifuge to be 12000r/min, and vacuum drying at normal temperature for 24h to obtain dry gelatin short fibers with the average length of 17 μm;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the step is the same as the first embodiment;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: the flow rate of electrostatic spinning in the steps (1) and (2) is increased from 1mL/h to 5mL/h, the rotating speed of an emulsifying machine is 10000r/min, and the dosage of other reagents and the operation condition are not changed. The average diameter of the finally obtained gelatin short fiber is 630nm, and the average length is 25 μm; the gelling time of the fiber composite in-situ pore-forming hydrogel is 80s, the storage modulus is 1.5kPa, and the porosity is 67%.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) preparing a gelatin fiber membrane:
dissolving gelatin in hexafluoroisopropanol to prepare a gelatin spinning solution with the concentration of 0.1 g/mL; absorbing the spinning solution by using an injector, placing the spinning solution on a propelling table of an electrostatic spinning machine, connecting with an 8kv high-voltage power supply, receiving by using a tin foil paper as a receiving device, wherein the receiving distance is 6cm, the flow rate is 10mL/h, and the drying is carried out in vacuum at normal temperature for 24h to obtain a dry gelatin fiber membrane, and the average diameter of the fiber is 550 nm;
(2) preparing gelatin short fibers:
placing the gelatin fiber membrane in a beaker filled with ethanol, shearing by a high-shear emulsifying machine, crushing the gelatin fiber membrane to prepare gelatin short fibers, wherein the rotating speed of the emulsifying machine is 15000r/min, and the treatment time is 15 min; centrifuging for 10min to remove ethanol, controlling the rotation speed of a centrifuge to be 12000r/min, and vacuum drying at normal temperature for 24h to obtain dry gelatin short fibers with the average length of 17 μm;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the step is the same as the first embodiment;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: the flow rate of electrostatic spinning in the steps (1) and (2) is increased from 1mL/h to 10mL/h, the rotating speed of the emulsifying machine is 15000r/min, and the dosage of other reagents and the operation condition are not changed. The average diameter of the finally obtained gelatin short fiber is 870nm, and the average length is 22 μm; the gelling time of the fiber composite in-situ pore-forming hydrogel is 60s, the storage modulus is 1.8kPa, and the porosity is 54%.
Fig. 1 is a flow chart of a method for constructing the fiber composite in-situ pore-forming injectable hydrogel according to the embodiment. Wherein (a) in fig. 1 is electrospun to prepare a gelatin film; (b) high shearing treatment to obtain gelatin short fiber; (c) glutaraldehyde cross-linked gelatin staple fibers; (d) compounding fiber with in-situ pore-forming hydrogel; (e) the gelatin microsphere is dissolved out at 37 ℃, and the gelatin short fiber plays a mechanical reinforcing role.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) preparing a gelatin fiber membrane:
dissolving gelatin in hexafluoroisopropanol to prepare a gelatin spinning solution with the concentration of 0.15 g/mL; absorbing the spinning solution by using an injector, placing the spinning solution on a propelling table of an electrostatic spinning machine, connecting with an 8kv high-voltage power supply, receiving by using a tin foil paper as a receiving device, wherein the receiving distance is 6cm, the flow rate is 1mL/h, and the drying is carried out in vacuum at normal temperature for 24h to obtain a dry gelatin fiber membrane, and the average diameter of the fiber is 550 nm;
(2) preparing gelatin short fibers:
placing the gelatin fiber membrane in a beaker filled with ethanol, shearing by a high-shear emulsifying machine, crushing the gelatin fiber membrane to prepare gelatin short fibers, wherein the rotating speed of the emulsifying machine is 25000r/min, and the treatment time is 15 min; centrifuging for 10min to remove ethanol, controlling the rotation speed of a centrifuge to be 12000r/min, and vacuum drying at normal temperature for 24h to obtain dry gelatin short fibers with the average length of 17 μm;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the step is the same as the first embodiment;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: the concentration of the gelatin spinning solution in the steps (1) and (2) is increased from 0.1g/mL to 0.15g/mL, the rotating speed of an emulsifying machine is 25000r/min, and the dosage of other reagents and the operation condition are not changed. The average diameter of the finally obtained gelatin short fibers is 690nm, and the average length is 9 mu m; the gelling time of the fiber composite in-situ pore-forming hydrogel is 75s, the storage modulus is 1.6kPa, and the porosity is 65%.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example five:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) preparing a gelatin fiber membrane:
dissolving gelatin in hexafluoroisopropanol to prepare a gelatin spinning solution with the concentration of 0.2 g/mL; absorbing the spinning solution by using an injector, placing the spinning solution on a propelling table of an electrostatic spinning machine, connecting with an 8kv high-voltage power supply, receiving by using a tin foil paper as a receiving device, wherein the receiving distance is 6cm, the flow rate is 1mL/h, and the drying is carried out in vacuum at normal temperature for 24h to obtain a dry gelatin fiber membrane, and the average diameter of the fiber is 550 nm;
(2) preparing gelatin short fibers:
placing the gelatin fiber membrane in a beaker filled with ethanol, shearing by a high-shear emulsifying machine, crushing the gelatin fiber membrane to prepare gelatin short fibers, wherein the rotating speed of the emulsifying machine is 22000r/min, and the treatment time is 15 min; centrifuging for 10min to remove ethanol, controlling the rotation speed of a centrifuge to be 12000r/min, and vacuum drying at normal temperature for 24h to obtain dry gelatin short fibers with the average length of 17 μm;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the step is the same as the first embodiment;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: the concentration of the gelatin spinning solution in the steps (1) and (2) is increased from 0.1g/mL to 0.2g/mL, the rotating speed of an emulsifying machine is 22000r/min, and the dosage of other reagents and the operation condition are not changed. The average diameter of the finally obtained gelatin short fiber is 720nm, and the average length is 13 μm; the gelling time of the fiber composite in-situ pore-forming hydrogel is 65s, the storage modulus is 1.7kPa, and the porosity is 61%.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example six:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) the step is the same as the first embodiment;
(2) the step is the same as the first embodiment;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) mixing the gelatin microspheres obtained in the step (5) with the carboxymethyl chitosan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed first precursor solution as a component one, and mixing the crosslinked gelatin fibers obtained in the step (3) with the oxidized glucan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed second precursor solution as a component two; the content of the gelatin microspheres is 0.03g/mL, and the content of the crosslinked gelatin fibers is 0.03 g/mL;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: in the step (6), the content of the crosslinked gelatin fiber is increased from 0.01g/mL to 0.03g/mL, and the dosage of other reagents and the operation condition are not changed. The gelling time of the finally obtained fiber composite in-situ pore-forming hydrogel is 70s, the storage modulus is 1.9kPa, and the porosity is 58%.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
Example seven:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1, a method for preparing an injectable hydrogel by compounding polysaccharide-based fibers and in-situ pore-forming includes the following steps:
(1) the step is the same as the first embodiment;
(2) the step is the same as the first embodiment;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) mixing the gelatin microspheres obtained in the step (5) with the carboxymethyl chitosan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed first precursor solution as a component one, and mixing the crosslinked gelatin fibers obtained in the step (3) with the oxidized glucan precursor aqueous solution obtained in the step (4) to prepare a uniformly mixed second precursor solution as a component two; the content of the gelatin microspheres is 0.03g/mL, and the content of the crosslinked gelatin fibers is 0.05 g/mL;
(7) the procedure is the same as in the first embodiment.
The difference between the present embodiment and the first embodiment is: in the step (6), the content of the crosslinked gelatin fiber is increased from 0.01g/mL to 0.05g/mL, and the dosage of other reagents and the operation condition are not changed. The gelling time of the finally obtained fiber composite in-situ pore-forming hydrogel is 63s, the storage modulus is 2.3kPa, and the porosity is 52%.
In the method, a gelatin fiber membrane is prepared by electrostatic spinning, uniformly dispersed gelatin short fibers are obtained after high-speed shearing treatment, and then the gelatin short fibers are prepared by taking glutaraldehyde as a cross-linking agent; then, carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction. The gelatin microspheres are gradually dissolved out at 37 ℃, and the gelatin fibers play a mechanical reinforcing role.
In conclusion, the gelatin short fibers are prepared by electrostatic spinning and high-shear emulsifying machine treatment, and are prepared by taking glutaraldehyde as a crosslinking agent. Carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, temperature response soluble gelatin microspheres prepared by an emulsion method are used as pore-forming agents, short gelatin fibers are used as reinforcing agents, and the dextran/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel is constructed through Schiff base reaction. The fiber composite in-situ pore-forming injectable hydrogel has good application value in tissue engineering.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and all changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, so long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and inventive concept of the polysaccharide-based fiber composite in situ pore-forming injectable hydrogel and the preparation method thereof are not departed from the technical principle and inventive concept of the present invention.
Claims (8)
1. A preparation method of polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel is characterized by comprising the following steps: preparing a gelatin fiber membrane through electrostatic spinning, performing high-speed shearing treatment to obtain uniformly dispersed gelatin short fibers, and then preparing the gelatin short fibers by using glutaraldehyde as a crosslinking agent; then, preparing temperature response soluble gelatin microspheres as a pore-foaming agent by using polysaccharide as a hydrogel precursor and using an emulsion method; and then, taking gelatin short fibers as a reinforcing agent, and constructing polysaccharide-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction.
2. The preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 1, which is characterized in that: carboxymethyl chitosan and oxidized dextran are used as hydrogel precursors, and a temperature response soluble gelatin microsphere is prepared by an emulsion method and used as a pore-foaming agent; and then, taking gelatin short fibers as a reinforcing agent, and constructing the glucan/carboxymethyl chitosan-based gelatin fiber composite in-situ pore-forming injectable hydrogel through Schiff base reaction.
3. The preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 2, which is characterized by comprising the following steps:
a. preparing a gelatin fiber membrane:
dissolving gelatin in a hexafluoroisopropanol solution, preparing a gelatin spinning solution with the concentration of 0.05-0.5 g/mL, sucking the gelatin spinning solution by using an injector, placing the gelatin spinning solution on a propelling table of an electrostatic spinning machine, connecting a high-voltage power supply of 5-15 kV, receiving electrostatic spinning by using tinfoil paper as a receiving device, wherein the receiving distance is 3-9 cm, and the flow rate is 1-10 mL/h, so as to obtain a gelatin fiber membrane; vacuum drying at normal temperature for at least 24h to obtain dry gelatin fiber membrane; the average diameter of the fibers is 500-1000 nm;
b. preparing gelatin short fibers:
b, placing the gelatin fiber membrane obtained in the step a into a beaker filled with ethanol, shearing the gelatin fiber membrane through a high-shear emulsifying machine, and smashing the gelatin fiber membrane to prepare gelatin short fibers; controlling the rotating speed of the emulsifying machine to be 5000-25000 r/min, and controlling the treatment time to be 15-30 min; then centrifuging for at least 20min, removing ethanol, and carrying out vacuum drying at normal temperature for at least 24h to obtain gelatin short fibers with the length of 9-30 mu m;
c. preparation of crosslinked gelatin short fiber:
taking 50mg of the gelatin short fiber obtained in the step b, uniformly dispersing the gelatin short fiber in 5mL of mixed solution of glutaraldehyde and ethanol, stirring at room temperature, carrying out crosslinking reaction for 15-30 min, then carrying out centrifugal treatment on a crosslinking product, washing with absolute ethanol for at least three times, and then drying the cleaned crosslinking product for at least 24h under the conditions of normal temperature and vacuum to obtain the crosslinked gelatin short fiber;
d. uniformly mixing a gelatin microsphere pore-foaming agent with the diameter of 100-400 mu m with a carboxymethyl chitosan precursor solution to obtain a component I; uniformly mixing the crosslinked gelatin fiber obtained in the step c and the oxidized dextran precursor solution to obtain a second component; in the component I, the content of the gelatin microsphere pore-forming agent is not less than 0.03 g/mL; in the second component, the content of the crosslinked gelatin short fiber is 0.01-0.05 g/mL; the molar ratio of aldehyde groups in the oxidized glucan to amino groups in the carboxymethyl chitosan is 1: 1, the total concentration of the oxidized dextran and the carboxymethyl chitosan as a high-molecular precursor is not lower than 3 percent;
e. and d, respectively filling the two solutions of the two components obtained in the step d into two syringes of a double-syringe injector, injecting the two solutions into a mold, forming hydrogel after 30-300 s, and finally placing the hydrogel at a temperature of not higher than 37 ℃ for at least 72h until gelatin microspheres are dissolved out, thereby obtaining the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel.
4. The preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 3, which is characterized in that: and in the step b, controlling the rotating speed of the centrifuge to be at least 12000r/min for centrifugal treatment.
5. The preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 3, which is characterized in that: in the step c, the mass percentage concentration of the glutaraldehyde in the mixed solution of the glutaraldehyde and the ethanol is 0.1-0.5%.
6. The preparation method of the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 3, which is characterized in that: in the step d, the amino content in the carboxymethyl chitosan is not lower than 3.4 mmol/g; the content of aldehyde groups in the oxidized glucan is not less than 4 mmol/g.
7. The polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel is characterized in that: the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel is prepared by the method for preparing the polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 1, and cross-linked gelatin short fibers are introduced into an in-situ pore-forming polysaccharide-based hydrogel system to form a fiber reinforced material.
8. The polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel according to claim 7, which is characterized in that: the storage modulus is 0.5-5 kPa, and the porosity is 60-95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010503242.8A CN111803707A (en) | 2020-06-05 | 2020-06-05 | Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010503242.8A CN111803707A (en) | 2020-06-05 | 2020-06-05 | Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111803707A true CN111803707A (en) | 2020-10-23 |
Family
ID=72848246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010503242.8A Pending CN111803707A (en) | 2020-06-05 | 2020-06-05 | Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111803707A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817214A (en) * | 2021-08-06 | 2021-12-21 | 广东省科学院健康医学研究所 | Porous hydrogel sponge and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264341A (en) * | 2008-04-11 | 2008-09-17 | 东华大学 | Three-dimensional porous tissue engineering bracket material, preparation and application thereof |
| CN102178980A (en) * | 2011-05-05 | 2011-09-14 | 东南大学 | Natural polymer composite porous fibrous scaffold and preparation method thereof |
| CN104487103A (en) * | 2012-05-15 | 2015-04-01 | 泰克尼恩研究和发展基金有限公司 | Fiber-reinforced hydrogel composites and methods of forming fiber-reinforced hydrogel composites |
| CN104479150A (en) * | 2014-10-29 | 2015-04-01 | 上海大学 | Preparation method of multiple cross-linked polysaccharide injectable hydrogel |
| US20160354515A1 (en) * | 2009-03-12 | 2016-12-08 | New Jersey Institute Of Technology | Scaffold for Tissue Growth and Repair |
| CN109157669A (en) * | 2018-09-18 | 2019-01-08 | 东华大学 | Cellulose enhances glucan base injectable anti-bacterial hydrogel dressing and preparation method thereof |
| CN110404083A (en) * | 2019-07-15 | 2019-11-05 | 浙江工业大学 | A kind of injection aquagel material and preparation method thereof, application |
-
2020
- 2020-06-05 CN CN202010503242.8A patent/CN111803707A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264341A (en) * | 2008-04-11 | 2008-09-17 | 东华大学 | Three-dimensional porous tissue engineering bracket material, preparation and application thereof |
| US20160354515A1 (en) * | 2009-03-12 | 2016-12-08 | New Jersey Institute Of Technology | Scaffold for Tissue Growth and Repair |
| CN102178980A (en) * | 2011-05-05 | 2011-09-14 | 东南大学 | Natural polymer composite porous fibrous scaffold and preparation method thereof |
| CN104487103A (en) * | 2012-05-15 | 2015-04-01 | 泰克尼恩研究和发展基金有限公司 | Fiber-reinforced hydrogel composites and methods of forming fiber-reinforced hydrogel composites |
| CN104479150A (en) * | 2014-10-29 | 2015-04-01 | 上海大学 | Preparation method of multiple cross-linked polysaccharide injectable hydrogel |
| CN109157669A (en) * | 2018-09-18 | 2019-01-08 | 东华大学 | Cellulose enhances glucan base injectable anti-bacterial hydrogel dressing and preparation method thereof |
| CN110404083A (en) * | 2019-07-15 | 2019-11-05 | 浙江工业大学 | A kind of injection aquagel material and preparation method thereof, application |
Non-Patent Citations (1)
| Title |
|---|
| 刘文: "《全国中医药行业高等教育"十三五"规划教材 药用高分子材料学》", 31 July 2017 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817214A (en) * | 2021-08-06 | 2021-12-21 | 广东省科学院健康医学研究所 | Porous hydrogel sponge and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104491914B (en) | A kind of porous pluralgel-nanofiber oxygen flow dressing and preparation method thereof | |
| Shen et al. | Comparison of hydrogels prepared with ionic-liquid-isolated vs commercial chitin and cellulose | |
| Rodríguez et al. | Electrospinning cellulosic nanofibers for biomedical applications: structure and in vitro biocompatibility | |
| KR101929661B1 (en) | Injectable composition for filler comprising porous biodegradable microspheres and water soluble natural polymers | |
| CN111588900B (en) | Waterproof breathable high-elastic self-repairing double-layer nanofiber membrane for skin dressing and preparation method thereof | |
| CN110772661A (en) | Nontoxic environment-friendly solvent type double-layer nanofiber skin dressing and preparation method thereof | |
| CN102178640B (en) | Method for loading hydrophobic medicament uniformly on hydrophilic polymer electrospinning nanofiber | |
| CN103285424A (en) | Three-dimensional fiber-based aerogel tissue engineering scaffold and preparation method thereof | |
| US20200330641A1 (en) | Biodegradable graphene oxide biocomposite fibrous membrane, preparation method and uses thereof | |
| CN110917386B (en) | Stem cell sponge scaffold, preparation method and application | |
| CN104511045A (en) | Polyvinyl alcohol/chitosan nano fiber film dressing containing nano silver and preparation thereof | |
| CN104436281A (en) | Preparation method of porous sodium alginate nano-fiber wound dressing | |
| CN112316914B (en) | Silk fibroin micro-nano fiber microsphere and preparation method and application thereof | |
| WO2020186715A1 (en) | Drug-loaded nanofiber film and preparation method and application thereof | |
| CN103272492B (en) | Enhanced-cellulose hollow fiber membrane and preparation method thereof | |
| CN109806771B (en) | Nanofiber-based composite hemodialysis membrane and preparation method thereof | |
| CN116803433B (en) | Medical dressing based on alginate and preparation method thereof | |
| CN111803707A (en) | Polysaccharide-based fiber composite in-situ pore-forming injectable hydrogel and preparation method thereof | |
| CN107670115A (en) | Fibroin albumen/hydroxyapatite/poly-（Racemic lactic acid co caprolactones）The preparation method of composite nano-fiber membrane | |
| WO2023179422A1 (en) | Elastic porous scaffold, preparation method therefor and use thereof | |
| Hu et al. | Recent Advances in Polysaccharide‐Based Physical Hydrogels and Their Potential Applications for Biomedical and Wastewater Treatment | |
| CN111962210A (en) | Polycaprolactone/methacryloylated elastin nanofiber composite membrane and preparation method and application thereof | |
| CN107875453A (en) | Carry preparation method of Types of Medicine electrostatic spinning guide tissue regeneration film and products thereof and application | |
| Zhang et al. | Cellulose nanofibers electrospun from aqueous conditions | |
| CN102441173A (en) | Preparation method of a drug release system with water-insoluble protein powder as drug carrier |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201023 |