CN108992707A - The preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel - Google Patents
The preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel Download PDFInfo
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- CN108992707A CN108992707A CN201811130489.9A CN201811130489A CN108992707A CN 108992707 A CN108992707 A CN 108992707A CN 201811130489 A CN201811130489 A CN 201811130489A CN 108992707 A CN108992707 A CN 108992707A
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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 kind of preparation methods of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel, first preparation chitosan-acetic acid solution and sodium β-glycerophosphate solution.Next takes 9ml chitosan-acetic acid solution to be put into beaker and is placed in 30 DEG C of constant temperature stirring water-baths, magnetic force moderate-speed mixer 5min, while being slowly added to 2.5% oyster shell nanometer hydroxyapatite powder, continues to stop stirring after stirring 0.5h, obtains water-setting collagen solution.Finally by water-setting collagen solution and sodium β-glycerophosphate solution while 15 min of ice bath, then the sodium β-glycerophosphate solution after 1ml ice bath is added dropwise in water-setting collagen solution, it is placed in 30 DEG C of constant temperature stirring water-baths, magnetic force moderate-speed mixer 10min is to get injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.Hydrogel prepared by the present invention has the characteristics that syringeability, Thermo-sensitive, safety non-toxic, can be used as bone renovating material.
Description
Technical field
The present invention relates to a kind of preparation methods of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel.
Background technique
Currently, bone will appear crackle under the influence ofs disease, traffic accident and athletic injury etc., fracture or be crushed, bone or soft
The wound or disease of bone tissue are especially easier to send out in the case where modernizing allegro life usually along with structural defect
It is raw, so to the attention in human body there is the Bone Defect Repari of social benefit and bone alternate material gradually to have obtained researcher.Mesh
Before, there are mainly three types of methods, respectively allogenic bone transplantation, autologous bone transplanting and use metal substitute material for clinical treatment bone defect
Material.For allogenic bone transplantation from a wealth of sources, main defect is to be easy to that immunological rejection effect or transmission occurs, and is not had
The autologous bone transplanting sources of these defects is again limited, and will cause new local disease damage, and as cannot be by body itself group
The metal material for knitting substitution is transplanted in human body situations such as will appear fatigue, fracture.These methods not only need to operate on to start
Art is even more to bring too many pain even sequelae for patient, therefore finding can be safe and nontoxic, effective, and is easy after transplanting
The bone renovating material of transplanting is of great significance.
For oyster shell as a seed oyster waste, calcium content is high, if cannot adequately utilize, not only waste of resource, and
And will cause certain environmental pollution, this patent uses oyster shell to prepare hydroxyapatite as raw material.Hydroxyapatite is not only
It is non-immunogenicity, nontoxic, it is often more important that it is with good osteoconductive potential and bioactivity, crystal structure and mineralising bone
Salt is similar [3].According to this performance, hydroxyapatite becomes receives the material of various concerns in recent years, main to apply
In bone renovating material and artificial tooth etc..And affirmative also clinically is made that its effect, researcher is also multi-party to its
The performance in face carried out deeper into research and development.
Chitosan (abbreviation cs) is a kind of positively charged alkaline polysaccharide, is the deacetylated production of chitin (Chitin)
Object, and chitin is mainly present in the crust of marine organisms, in shrimp shell, crab shell and fungal cell wall matrix, certainly
Rich reserves in right boundary, cost are again low.The structure of CS molecule is in chain, in molecule with a large amount of-OH ,-NH- and-NH2 and
Amide groups is easy to produce intermolecular and intramolecular hydrogen bond, forms the biomaterial with certain degree of cross linking.
Temperature-sensitive hydrogel refers to the material that sensitive response is generated to extraneous thermal stimulus, when the temperature varies, liquid
State generates a kind of not sustained mutations immediately, and occurs phase transition within a certain range, and liquid is transformed into hydrogel.With injectable
The hydrogel of property, Thermo-sensitive, safety non-toxic, can be used as bone renovating material.
Summary of the invention
It is an object of the invention to overcome the shortcomings of above-mentioned prior art, provide it is a kind of can as bone renovating material can
Inject the preparation method of chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel.
To achieve the goals above, the technical solution adopted by the present invention is that: a kind of injectable chitosan oyster shell hydroxyl phosphorus
The preparation method of lime stone temperature-sensitive hydrogel, characterized by the following steps:
S1: make the chitosan-acetic acid solution that solvent prepares 2.15%-2.00% with 0.1mol/L acetum, prepared with purified water
The sodium β-glycerophosphate solution of 5.8%-5.0%, and be put into refrigerator and save；
S2: taking 9ml chitosan-acetic acid solution to be put into the beaker of 20ml, then places the beaker in 30 DEG C of constant temperature stirring water-baths,
Magnetic force moderate-speed mixer 5min, while it being slowly added to oyster shell nanometer hydroxyapatite powder, continue to stop stirring after stirring 0.5h,
Obtain water-setting collagen solution, wherein oyster shell nanometer hydroxyapatite powder is 2.8%-- with the mass concentration ratio of entire hydrogel
2.0%；
S3: then water-setting collagen solution and sodium β-glycerophosphate solution while 15 min of ice bath add dropwise in water-setting collagen solution
Sodium β-glycerophosphate solution after entering 1ml ice bath is placed in 30 DEG C of constant temperature stirring water-baths, magnetic force moderate-speed mixer 10min to get
Injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.
Further, the preparation method of the oyster shell nanometer hydroxyapatite powder protects following steps: (1) weighing male
Oyster shells end 5g and diammonium hydrogen phosphate 7.92g, is put into 60mL reaction kettle liner, adds 30 mL deionized waters, be placed in magnetic force
It is sealed in reaction kettle after stirring 30 min on blender it being made to be evenly distributed；(2) it is reacted by hydrothermal synthesis reaction condition,
Temperature is 220 degrees Celsius, and the reaction time is 8 hours, wherein the suitable Ca/P molar ratio n (CaCO3) of hydrothermal synthesis: n
((NH4) 2HPO4) is 5:6, mass ratio 5:7.92；(3) after hydrothermal synthesis reaction, room is completely cooled down to reaction kettle
Temperature opens reaction kettle, takes out product, centrifugation 3 times is washed with deionized, then with dehydrated alcohol centrifuge washing 3 times, 80 degrees Celsius
Under it is obtained by drying arrive oyster shell nanometer hydroxyapatite.
Further, the oyster shell powder is prepared by the following method: (1) it picks choosing: picking and select oyster shell easy to clean,
Subsequent processing can be allowed more convenient；(2) it impregnates: impregnating 4 h with tap water, constantly agitation is washed；(3) it pickling: will wash
Net oyster shell is put in the hydrochloric acid of people 0.5%, constantly agitation pickling, is taken after 1 h；(4) it rinses: being rinsed, made with distilled water immersion
It reaches neutral；(5) it removes protein: appropriate 10% sodium hydroxide solution, 95 DEG C of water-bath 5 h of heating is added；(6) dry:
After cooling, then is eluted 3 times and dried with deionized water；(7) it is sieved: oyster shell is broken into pieces, it is finely ground, 200 meshes are crossed, oyster shell powder is obtained
End.
The beneficial effects of the present invention are: preparation method is easy to operate, answered by using hydroxyapatite and chitosan
It closes, sodium glycero-phosphate is added, prepare injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel, hydrogel tool
There is the characteristics of syringeability, Thermo-sensitive, safety non-toxic, bone renovating material, wide market can be used as.
Specific embodiment
A kind of preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel of the present invention, including it is as follows
Step: S1: make the chitosan-acetic acid solution that solvent prepares 2.15%-2.00% with 0.1mol/L acetum, prepared with purified water
The sodium β-glycerophosphate solution of 5.8%-5.0%, and be put into refrigerator and save.
S2: taking 9ml chitosan-acetic acid solution to be put into the beaker of 20ml, then places the beaker 30 DEG C of constant temperature stirring water-baths
In, magnetic force moderate-speed mixer 5min, while it being slowly added to oyster shell nanometer hydroxyapatite powder, continue to stop stirring after stirring 0.5h
It mixes, obtains water-setting collagen solution, wherein oyster shell nanometer hydroxyapatite powder is with the mass concentration ratio of entire water-setting collagen solution
2.8%--2.0%。
S3: by water-setting collagen solution and sodium β-glycerophosphate solution 15 min of ice bath simultaneously, then in water-setting collagen solution by
Sodium β-glycerophosphate solution after being added dropwise to 1ml ice bath is placed in 30 DEG C of constant temperature stirring water-baths, magnetic force moderate-speed mixer 10min,
Up to injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.
Specifically, the preparation method of above-mentioned oyster shell nanometer hydroxyapatite powder protects following steps:
(1) oyster shell powder 5g and diammonium hydrogen phosphate 7.92g are weighed, is put into 60mL reaction kettle liner, add 30 mL go from
Sub- water is placed on magnetic stirring apparatus after stirring 30 min it being made to be evenly distributed and is sealed in reaction kettle；
(2) it is reacted by hydrothermal synthesis reaction condition, temperature is 220 degrees Celsius, and the reaction time is 8 hours, wherein hydro-thermal is closed
At suitable Ca/P molar ratio n (CaCO3): n ((NH4) 2HPO4) be 5:6, mass ratio 5:7.92；
(3) after hydrothermal synthesis reaction, it is completely cooled down to room temperature to reaction kettle, opens reaction kettle, product is taken out, uses deionization
Water washing is centrifuged 3 times, then arrives oyster shell nano-hydroxy-apatite with obtained by drying under dehydrated alcohol centrifuge washing 3 times, 80 degrees Celsius
Stone.
Wherein, the oyster shell powder is prepared by the following method: (1) picking choosing: picking and select oyster shell easy to clean, can allow
Subsequent processing is more convenient；(2) it impregnates: impregnating 4 h with tap water, constantly agitation is washed；(3) pickling: by what is cleaned
Oyster shell is put in the hydrochloric acid of people 0.5%, constantly agitation pickling, is taken after 1 h；(4) it rinses: being rinsed with distilled water immersion, reach it
To neutrality；(5) it removes protein: appropriate 10% sodium hydroxide solution is added, 95 DEG C of water-bath 5 h of heating will be in oyster shell
Protein removal；(6) dry: after cooling, then to be eluted 3 times and dried with deionized water；(7) it is sieved: oyster shell is broken into pieces, it is finely ground,
200 meshes are crossed, oyster shell powder is obtained.
The above content is merely illustrative of the technical solution of the present invention, and those skilled in the art are to technology of the invention
The simple modification or equivalent replacement that scheme carries out, all without departing from the spirit and scope of technical solution of the present invention.
Claims (3)
1. a kind of preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel, it is characterised in that: including
Following steps:
S1: make the chitosan-acetic acid solution that solvent prepares 2.15%-2.00% with 0.1mol/L acetum, prepared with purified water
The sodium β-glycerophosphate solution of 5.8%-5.0%, and be put into refrigerator and save；
S2: taking 9ml chitosan-acetic acid solution to be put into the beaker of 20ml, then places the beaker in 30 DEG C of constant temperature stirring water-baths,
Magnetic force moderate-speed mixer 5min, while it being slowly added to oyster shell nanometer hydroxyapatite powder, continue to stop stirring after stirring 0.5h,
Obtain water-setting collagen solution, wherein oyster shell nanometer hydroxyapatite powder is with the mass concentration ratio of entire water-setting collagen solution
2.8%--2.0%；
S3: then water-setting collagen solution and sodium β-glycerophosphate solution while 15 min of ice bath add dropwise in water-setting collagen solution
Sodium β-glycerophosphate solution after entering 1ml ice bath is placed in 30 DEG C of constant temperature stirring water-baths, magnetic force moderate-speed mixer 10min to get
Injectable chitosan/oyster shell hydroxyapatite temperature-sensitive hydrogel.
2. the preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel according to claim 1,
It is characterized by: the preparation method of the oyster shell nanometer hydroxyapatite powder protects following steps:
(1) oyster shell powder 5g and diammonium hydrogen phosphate 7.92g are weighed, is put into 60mL reaction kettle liner, add 30 mL go from
Sub- water is placed on magnetic stirring apparatus after stirring 30 min it being made to be evenly distributed and is sealed in reaction kettle；
(2) it is reacted by hydrothermal synthesis reaction condition, temperature is 220 degrees Celsius, and the reaction time is 8 hours, wherein hydro-thermal is closed
At suitable Ca/P molar ratio n (CaCO3): n ((NH4) 2HPO4) be 5:6, mass ratio 5:7.92；
(3) after hydrothermal synthesis reaction, it is completely cooled down to room temperature to reaction kettle, opens reaction kettle, product is taken out, uses deionization
Water washing is centrifuged 3 times, then arrives oyster shell nano-hydroxy-apatite with obtained by drying under dehydrated alcohol centrifuge washing 3 times, 80 degrees Celsius
Stone, then oyster shell nanometer hydroxyapatite powder is obtained after 900 degree are calcined 8 hours.
3. the preparation method of injectable chitosan oyster shell hydroxyapatite temperature-sensitive hydrogel according to claim 2,
It is characterized by: the oyster shell powder is prepared by the following method:
(1) it picks choosing: picking and select oyster shell easy to clean, subsequent processing can be allowed more convenient；
(2) it impregnates: impregnating 4 h with tap water, constantly agitation is washed；
(3) pickling: clean oyster shell is put in the hydrochloric acid of people 0.5%, constantly agitation pickling, is taken after 1 h；
(4) it rinses: being rinsed with distilled water immersion, reach neutrality；
(5) it removes protein: appropriate 10% sodium hydroxide solution, 95 DEG C of water-bath 5 h of heating is added；
(6) dry: after cooling, then to be eluted 3 times and dried with deionized water；
(7) it is sieved: oyster shell is broken into pieces, it is finely ground, 200 meshes are crossed, oyster shell powder is obtained.
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| CN111744557A (en) * | 2020-07-07 | 2020-10-09 | 广东海洋大学 | Nano-hydroxyapatite/N-maleylation chitosan composite material and preparation method and application thereof |
| CN112869174A (en) * | 2021-02-04 | 2021-06-01 | 海南热带海洋学院 | Oyster calcium emulsion and preparation method thereof |
| CN115028150A (en) * | 2022-07-15 | 2022-09-09 | 中国地质大学（北京） | Preparation method and application of synthetic hydroxyapatite |
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| CN112869174A (en) * | 2021-02-04 | 2021-06-01 | 海南热带海洋学院 | Oyster calcium emulsion and preparation method thereof |
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