CN108992707B - Preparation method of injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel - Google Patents
Preparation method of injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel Download PDFInfo
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- CN108992707B CN108992707B CN201811130489.9A CN201811130489A CN108992707B CN 108992707 B CN108992707 B CN 108992707B CN 201811130489 A CN201811130489 A CN 201811130489A CN 108992707 B CN108992707 B CN 108992707B
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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
- A61L27/20—Polysaccharides
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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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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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
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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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- 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
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention discloses a preparation method of injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel, which comprises the steps of preparing chitosan acetic acid solution and beta-sodium glycerophosphate solution. And secondly, putting 9ml of chitosan acetic acid solution into a beaker, placing the beaker into a constant-temperature stirring water bath kettle at the temperature of 30 ℃, stirring at medium speed for 5min by magnetic force, slowly adding 2.5% of oyster shell nano-hydroxyapatite powder, continuously stirring for 0.5h, and stopping stirring to obtain a hydrogel stock solution. And finally, simultaneously carrying out ice bath on the hydraulic collagen liquid and the beta-sodium glycerophosphate solution for 15 min, then dropwise adding 1ml of the ice-bath beta-sodium glycerophosphate solution into the hydraulic collagen liquid, placing the mixture into a constant-temperature stirring water bath kettle at the temperature of 30 ℃, and stirring at a medium speed for 10min under a magnetic force to obtain the injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel. The hydrogel prepared by the invention has the characteristics of injectability, temperature sensitivity, safety and no toxicity, and can be used as a bone repair material.
Description
Technical Field
The invention relates to a preparation method of an injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel.
Background
At present, bones are cracked, broken or broken under the influence of diseases, car accidents, sports injuries and the like, and injuries or diseases of bones or cartilage tissues are usually accompanied by structural defects and are more likely to occur particularly in modern fast-paced life, so that researchers pay attention to bone repair and bone substitute materials with social benefits for human bodies. Currently, there are three main methods for clinical treatment of bone defects, including allogeneic bone grafting, autologous bone grafting and the use of metal substitute materials. For allogeneic bone transplantation with wide sources, the main defect is that immunological rejection or disease transmission is easy to occur, autologous bone transplantation without the defects has limited sources and can cause new local lesions, and fatigue, fracture and other situations can occur when the autologous bone transplantation is transplanted into a human body as a metal material which cannot be replaced by the body tissue. The methods not only need operation, but also bring much pain and even sequelae to patients after transplantation, so that the finding of the bone repair material which is safe, nontoxic, effective and easy to transplant has important significance.
Oyster shell is as an oyster discarded object, and calcium content is high, if can not obtain abundant utilization, not only the resource of wasting, can cause certain environmental pollution moreover, this patent is with oyster shell as raw materials preparation hydroxyapatite. Hydroxyapatite is not only non-immunogenic and non-toxic, but also has good bone conduction ability and bioactivity, and the crystal structure of the hydroxyapatite is similar to that of mineralized bone salt [3 ]. According to this property, hydroxyapatite has been attracting much attention in recent years, and is mainly used for bone repair materials, artificial teeth, and the like. The effect of the composition is also confirmed clinically, and researchers also carry out more intensive research and development on various performances of the composition.
Chitosan (cs) is a basic polysaccharide with positive charges, and is a deacetylation product of Chitin (Chitin), and the Chitin mainly exists in shells of marine organisms, such as shrimp shells, crab shells and fungal cell wall matrixes, and is abundant in nature and low in cost. The CS molecules are in a chain shape, and the molecules are provided with a large amount of-OH, -NH-and-NH 2 and amide groups, so that intermolecular and intramolecular hydrogen bonds are easily generated, and the biological material with a certain crosslinking degree is formed.
The temperature-sensitive hydrogel is a material which generates sensitive response to external temperature stimulation, when the temperature changes, the liquid state immediately generates a discontinuous mutation, and phase transformation occurs in a certain range, so that the liquid state is transformed into the hydrogel. The hydrogel has injectability, temperature sensitivity, safety and no toxicity, and can be used as a bone repair material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel which can be used as a bone repair material.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of an injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing 2.15-2.00% chitosan acetic acid solution by using 0.1mol/L acetic acid solution as a solvent, preparing 5.8-5.0% beta-sodium glycerophosphate solution by using purified water, and storing in a refrigerator;
s2: putting 9ml of chitosan acetic acid solution into a 20ml beaker, putting the beaker into a 30 ℃ constant-temperature stirring water bath kettle, stirring at a medium speed for 5min by magnetic force, slowly adding the oyster shell nano-hydroxyapatite powder, continuously stirring for 0.5h, and stopping stirring to obtain the hydrogel collagen liquid, wherein the mass concentration ratio of the oyster shell nano-hydroxyapatite powder to the whole hydrogel is 2.8% -2.0%;
s3: and (3) carrying out ice-bath on the hydraulic collagen liquid and the beta-sodium glycerophosphate solution for 15 min at the same time, then dropwise adding 1ml of the ice-bath beta-sodium glycerophosphate solution into the hydraulic collagen liquid, placing the mixture into a constant-temperature stirring water bath kettle at the temperature of 30 ℃, and stirring at a medium speed for 10min by magnetic force to obtain the injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.
Further, the preparation method of the oyster shell nano-hydroxyapatite powder comprises the following steps: (1) weighing 5g of oyster shell powder and 7.92g of diammonium hydrogen phosphate, putting the oyster shell powder and the diammonium hydrogen phosphate into a 60mL inner container of a reaction kettle, adding 30 mL of deionized water, putting the mixture on a magnetic stirrer, stirring for 30 min to ensure that the mixture is uniformly distributed, and then sealing the mixture in the reaction kettle; (2) carrying out reaction according to hydrothermal synthesis reaction conditions, wherein the temperature is 220 ℃, and the reaction time is 8 hours, wherein the appropriate Ca/P molar ratio n (CaCO3) to n ((NH4)2HPO4) for hydrothermal synthesis is 5:6, and the mass ratio is 5: 7.92; (3) after the hydrothermal synthesis reaction is finished, after the reaction kettle is completely cooled to room temperature, opening the reaction kettle, taking out a product, washing and centrifuging for 3 times by using deionized water, then washing and centrifuging for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the oyster shell nano-hydroxyapatite.
Further, the oyster shell powder is prepared by the following method: (1) picking: oyster shells which are easy to clean are picked, so that the subsequent treatment is more convenient; (2) soaking: soaking in tap water for 4 h, and washing with water under constant stirring; (3) acid washing: washing cleaned Concha Ostreae with 0.5% hydrochloric acid under stirring for 1 hr; (4) rinsing: soaking and rinsing with distilled water to make it neutral; (5) removing proteins: adding a proper amount of 10% sodium hydroxide solution, and heating for 5h in a water bath at 95 ℃; (6) and (3) drying: after cooling, leaching for 3 times by using deionized water and airing; (7) sieving: the oyster shell is broken and ground, and is sieved by a 200-mesh sieve to obtain oyster shell powder.
The invention has the beneficial effects that: the preparation method is simple to operate, the injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel is prepared by compounding the hydroxyapatite and the chitosan and adding the sodium glycerophosphate, and the hydrogel has the characteristics of injectability, temperature sensitivity, safety and no toxicity, can be used as a bone repair material, and has a wide market prospect.
Detailed Description
The invention relates to a preparation method of an injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel, which comprises the following steps: s1: 0.1mol/L acetic acid solution is used as a solvent to prepare 2.15 to 2.00 percent chitosan acetic acid solution, purified water is used to prepare 5.8 to 5.0 percent beta-sodium glycerophosphate solution, and the solution is put into a refrigerator for storage.
S2: putting 9ml of chitosan acetic acid solution into a 20ml beaker, putting the beaker into a 30 ℃ constant-temperature stirring water bath kettle, stirring at a medium speed for 5min by magnetic force, slowly adding the oyster shell nano-hydroxyapatite powder, continuously stirring for 0.5h, and stopping stirring to obtain the hydrogel collagen liquid, wherein the mass concentration ratio of the oyster shell nano-hydroxyapatite powder to the whole hydrogel collagen liquid is 2.8% -2.0%.
S3: and (3) carrying out ice-bath on the hydraulic collagen liquid and the beta-sodium glycerophosphate solution for 15 min at the same time, then dropwise adding 1ml of the ice-bath beta-sodium glycerophosphate solution into the hydraulic collagen liquid, placing the mixture into a constant-temperature stirring water bath kettle at the temperature of 30 ℃, and stirring at a medium speed for 10min by magnetic force to obtain the injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.
Specifically, the preparation method of the oyster shell nano-hydroxyapatite powder comprises the following steps:
(1) weighing 5g of oyster shell powder and 7.92g of diammonium hydrogen phosphate, putting the oyster shell powder and the diammonium hydrogen phosphate into a 60mL inner container of a reaction kettle, adding 30 mL of deionized water, putting the mixture on a magnetic stirrer, stirring for 30 min to ensure that the mixture is uniformly distributed, and then sealing the mixture in the reaction kettle;
(2) carrying out reaction according to hydrothermal synthesis reaction conditions, wherein the temperature is 220 ℃, and the reaction time is 8 hours, wherein the appropriate Ca/P molar ratio n (CaCO3) to n ((NH4)2HPO4) for hydrothermal synthesis is 5:6, and the mass ratio is 5: 7.92;
(3) after the hydrothermal synthesis reaction is finished, after the reaction kettle is completely cooled to room temperature, opening the reaction kettle, taking out a product, washing and centrifuging for 3 times by using deionized water, then washing and centrifuging for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the oyster shell nano-hydroxyapatite.
Wherein the oyster shell powder is prepared by the following method: (1) picking: oyster shells which are easy to clean are picked, so that the subsequent treatment is more convenient; (2) soaking: soaking in tap water for 4 h, and washing with water under constant stirring; (3) acid washing: washing cleaned Concha Ostreae with 0.5% hydrochloric acid under stirring for 1 hr; (4) rinsing: soaking and rinsing with distilled water to make it neutral; (5) removing proteins: adding a proper amount of 10% sodium hydroxide solution, heating in water bath at 95 deg.C for 5h to remove protein in Concha Ostreae; (6) and (3) drying: after cooling, leaching for 3 times by using deionized water and airing; (7) sieving: the oyster shell is broken and ground, and is sieved by a 200-mesh sieve to obtain oyster shell powder.
The above description is only for the purpose of illustrating the technical solutions of the present invention, and those skilled in the art can make simple modifications or equivalent substitutions on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (2)
1. A preparation method of an injectable chitosan oyster shell hydroxyapatite temperature sensitive hydrogel is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing 2.15-2.00% chitosan acetic acid solution by using 0.1mol/L acetic acid solution as a solvent, preparing 5.8-5.0% beta-sodium glycerophosphate solution by using purified water, and storing in a refrigerator;
s2: putting 9mL of chitosan acetic acid solution into a 20mL beaker, putting the beaker into a 30 ℃ constant-temperature stirring water bath kettle, stirring at a magnetic force medium speed for 5min, slowly adding oyster shell nano-hydroxyapatite powder, continuously stirring for 0.5h, and stopping stirring to obtain a hydrogel collagen liquid, wherein the mass concentration ratio of the oyster shell nano-hydroxyapatite powder to the whole hydrogel collagen liquid is 2.8-2.0%;
s3: simultaneously ice-bathing the hydraulic collagen liquid and the beta-sodium glycerophosphate solution for 15 min, then dropwise adding 1mL of the ice-bathed beta-sodium glycerophosphate solution into the hydraulic collagen liquid, placing the mixture into a constant-temperature stirring water bath kettle at the temperature of 30 ℃, and stirring at a medium speed and a magnetic force for 10min to obtain the injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel;
the preparation method of the oyster shell nano-hydroxyapatite powder comprises the following steps:
(1) weighing 5g of oyster shell powder and 7.92g of diammonium hydrogen phosphate, putting the oyster shell powder and the diammonium hydrogen phosphate into a 60mL inner container of a reaction kettle, adding 30 mL of deionized water, putting the mixture on a magnetic stirrer, stirring for 30 min to ensure that the mixture is uniformly distributed, and then sealing the mixture in the reaction kettle;
(2) the reaction is carried out according to the reaction conditions of hydrothermal synthesis, the temperature is 220 ℃, the reaction time is 8 hours, wherein, the appropriate Ca/P molar ratio n (CaCO) of the hydrothermal synthesis3)∶n((NH4)2HPO4) Is 5:6, the mass ratio is 5: 7.92;
(3) after the hydrothermal synthesis reaction is finished, the reaction kettle is opened after being completely cooled to room temperature, the product is taken out, washed and centrifuged for 3 times by deionized water, then washed and centrifuged for 3 times by absolute ethyl alcohol, dried at 80 ℃ to obtain the oyster shell nano-hydroxyapatite, and calcined at 900 ℃ for 8 hours to obtain the oyster shell nano-hydroxyapatite powder.
2. The method for preparing injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel according to claim 1, characterized in that: the oyster shell powder is prepared by the following method:
(1) picking: oyster shells which are easy to clean are picked, so that the subsequent treatment is more convenient;
(2) soaking: soaking in tap water for 4 h, and washing with water under constant stirring;
(3) acid washing: washing cleaned Concha Ostreae with 0.5% hydrochloric acid under stirring for 1 hr;
(4) rinsing: soaking and rinsing with distilled water to make it neutral;
(5) removing proteins: adding a proper amount of 10% sodium hydroxide solution, and heating for 5h in a water bath at 95 ℃;
(6) and (3) drying: after cooling, leaching for 3 times by using deionized water and airing;
(7) sieving: the oyster shell is broken and ground, and is sieved by a 200-mesh sieve to obtain oyster shell powder.
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CN109568665B (en) * | 2018-12-28 | 2021-12-10 | 中国医科大学附属第一医院 | Temperature-sensitive injectable hydrogel loaded with adipose-derived stem cell exosomes and preparation method and application thereof |
CN110755627A (en) * | 2019-12-02 | 2020-02-07 | 北京福原科技有限公司 | Temperature-sensitive drug delivery material in liquid state at 4 ℃ and solid state at 37 DEG C |
CN111744557B (en) * | 2020-07-07 | 2021-03-12 | 广东海洋大学 | Nano-hydroxyapatite/N-maleylation chitosan composite material and preparation method and application thereof |
CN112869174B (en) * | 2021-02-04 | 2023-05-02 | 海南热带海洋学院 | Oyster calcium emulsion and preparation method thereof |
CN115028150B (en) * | 2022-07-15 | 2023-07-04 | 中国地质大学(北京) | Preparation method and application of synthetic hydroxyapatite |
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