CN109481733A - A kind of composite coating and preparation method thereof for Bone Defect Repari - Google Patents

A kind of composite coating and preparation method thereof for Bone Defect Repari Download PDF

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Publication number
CN109481733A
CN109481733A CN201811640011.0A CN201811640011A CN109481733A CN 109481733 A CN109481733 A CN 109481733A CN 201811640011 A CN201811640011 A CN 201811640011A CN 109481733 A CN109481733 A CN 109481733A
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China
Prior art keywords
preparation
composite coating
bone defect
defect repari
gelatin
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Pending
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CN201811640011.0A
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Chinese (zh)
Inventor
周青宇
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Sichuan Chronoswiss Biological Polytron Technologies Inc
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Sichuan Chronoswiss Biological Polytron Technologies Inc
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Priority to CN201811640011.0A priority Critical patent/CN109481733A/en
Publication of CN109481733A publication Critical patent/CN109481733A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/34Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/18Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/04Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The composite coating and preparation method thereof that the invention discloses a kind of for Bone Defect Repari, is related to biomedical materials field, and a kind of composite coating for Bone Defect Repari includes gelatin and hydroxyapatite, and gelatin surface is provided with hydroxyl or amino;The coating contacts angle is 40 ~ 80 °, and tensile strength is 30 ~ 50MPa.The preparation method of the composite coating of Bone Defect Repari, comprising the following steps: (1) preparation of gelatin, the preparation of (2) hydroxyapatite;(3) graft reaction: gelatin and hydroxyapatite are sufficiently mixed by good solvent, and crosslinking agent is added, and reaction obtains finished product at a certain temperature.The composite coating hydrophily that the present invention is prepared is stronger, improves contact angle and tensile strength, increases the interface binding power between coating and matrix, it is made to be firmly fixed at material surface.

Description

A kind of composite coating and preparation method thereof for Bone Defect Repari
Technical field
The present invention relates to biomedical materials fields, especially a kind of for the composite coating of Bone Defect Repari and its preparation side Method.
Background technique
Natural bone tissue mainly includes with hydroxyapatite inorganic phase as main component and the organic phase based on collagen. And nanometer Hap(hydroxyapatite) closely similar with the inorganic constituents of nature bone, there is excellent bioactivity and osteoconductive, It is thus considered as the ideal material of bone tissue engineer.But its mechanical property is poor when pure inorganic HAp is used as biomaterial, It cannot be used for the stress support at load-bearing bone, while HAp only has osteoconductive, be unfavorable for promoting after it is implanted into bone defect position Into the depth and quantity of new Bone Ingrowth, therefore, simple HAp material is difficult to repair the bone defect of pathological state or large volume, i.e., Osteoinductive is poor.
Gelatin is the collagenous portion hydrolysate and a kind of protein of skin, bone, cartilage and ligament, have with The identical amino acid of collagen shows good biocompatibility and weaker antigenicity, while also having preferable cell viscous Attached effect and osteoinductive, but its absorption is too fast and mechanical performance is poor.The two is carried out compound, that is, synthesizes compound painting Material, can be improved biocompatibility, engineering properties and osteoinductive.Therefore, composite coating is carried out to bone holder material surface Processing, so as to improve the compatibility of bone holder material.It is compound using various composition, construct the bio-medical material with excellent performance Material, the gelatin and hydroxyapatite closely similar with natural bone tissue are introduced into material surface simultaneously, make its have both raw material and The advantage of coating material.
In the prior art, Chinese patent CN 104404480 discloses a kind of Mg alloy surface and prepares hydroxyapatite and bone Collagen meets the method for coating, the preparation including deposition solution, and the concentration of calcium nitrate is 0.02- in deposition solution 0.05mol/L, the concentration of sodium phosphate are 0.002-0.005mol/L, and the concentration of bone collagen is 0.5-2.0g/L, are deposited molten The pH value of liquid is 3.0-4.0, and magnesium alloy is cleaned by ultrasonic 8-10min after grinding process in alcohol and acetone, then will Magnesium alloy, which is placed in deposition liquid, deposits 6-24h, and the deposition initial stage uses power for 100-150W, and frequency is the super of 30 ~ 45KHz 5-15min is swung in acoustic shock.Preparation method of the present invention is simple, the degradation of preparation-obtained hydroxyapatite/bone collagen coating Speed is low, and the biological medical magnesium alloy with the coating has preferable corrosion resistance, and ossein egg is added in deposition solution It is white, the forming core of hydroxyapatite can be accelerated and grown up, the corrosion resistance of material is improved.
The composite coating being prepared is simply mixed in hydroxyapatite and bone collagen in the patent, gelatin is reunited Or conformational isomerism causes coating surface uneven, has apparent phenomenon of phase separation between HAp and gelatin continuous phase, makes coating More easily degrade.
Summary of the invention
Goal of the invention of the invention is: in view of the above problems, providing a kind of composite coating for Bone Defect Repari And preparation method thereof, the composite coating hydrophily that the present invention is prepared is more preferable, and it is more uniform that painting is located at bone material surface, into one The degradation cycle of the coating of step increases to 1 year.
The technical solution adopted by the invention is as follows:
A kind of composite coating for Bone Defect Repari, including gelatin and hydroxyapatite, the gelatin surface are provided with hydrophilic radical.
Further, the hydrophilic radical is hydroxyl or amino.
Further, the coating contacts angle is 40 ~ 80 °, and tensile strength is 30 ~ 50MPa.
A kind of preparation method of the composite coating for Bone Defect Repari, comprising the following steps:
(1) it the preparation of gelatin: chooses bone collagen and protease is added, it is 2 ~ 3 × 10 that reaction, which obtains molecular weight,4
(2) it the preparation of hydroxyapatite: weighs sufficiently dissolution in certain calcium nitrate addition distilled water and obtains the water-soluble of calcium nitrate Liquid, sodium phosphate is added into calcium nitrate aqueous solution, and strong stirring dissolves sodium phosphate sufficiently;
(3) graft reaction: gelatin and hydroxyapatite are sufficiently mixed by good solvent, crosslinking agent are added, in certain temperature Lower reaction obtains finished product.
Further, the good solvent in the step (3) includes one of water, tetrahydrofuran, ether.
Further, crosslinking agent described in the step (3) is one of ethanedioic acid, succinic acid, pimelic acid.
Further, gelatin, hydroxyapatite and crosslinking agent are mixed according to 5 ~ 8:5 of mass ratio ~ 10:2 ~ 4 in the step (3) It closes.
Further, the reaction temperature in the step (3) is 75 ~ 85 DEG C.
Further, crosslinking agent described in the step (3) is Geniposide, the gelatin, hydroxyapatite and Geniposide It is mixed according to 5 ~ 8:5 of mass ratio ~ 10:4 ~ 6.
Further, in the step (3), crosslinking temperature is 30 ~ 35 DEG C.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1, the present invention carries out the composite coating that grafting modification is prepared by the mixture to gelatin and hydroxyapatite Hydrophily is stronger, further improves contact angle and tensile strength, increases the interface binding power between coating and matrix, makes It is firmly fixed at material surface;
2, preparation method of the present invention is simple, and the coating being prepared can increase the biocompatibility on bone renovating material surface, Improve hydrophilic effect, is suitble to promote and apply;
3, for coating prepared by the present invention due to adsorptivity and good hydrophilic property, degradation speed is slower, further improves degradation cycle.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive Feature and/or step other than, can combine in any way.
Any feature disclosed in this specification (including any accessory claim, abstract), unless specifically stated, It is replaced by other equivalent or with similar purpose alternative features.That is, unless specifically stated, each feature is a series of An example in equivalent or similar characteristics.
Embodiment 1
A kind of composite coating for Bone Defect Repari, including gelatin and hydroxyapatite, which is characterized in that gelatin surface is provided with hydroxyl Base, coating contacts angle are 40 ~ 80 °, and tensile strength is 30 ~ 50MPa.
Embodiment 2
A kind of composite coating for Bone Defect Repari, including gelatin and hydroxyapatite, which is characterized in that gelatin surface is provided with ammonia Base, coating contacts angle are 40 ~ 80 °, and tensile strength is 30 ~ 50MPa.
Embodiment 3
A kind of preparation method of the composite coating for Bone Defect Repari, comprising the following steps:
(1) it the preparation of gelatin: chooses bone collagen and papain is added, it is 2 ~ 3 × 10 that reaction, which obtains molecular weight,4
(2) it the preparation of hydroxyapatite: weighs sufficiently dissolution in certain calcium nitrate addition distilled water and obtains calcium nitrate Aqueous solution, sodium phosphate is added into calcium nitrate aqueous solution, and strong stirring dissolves sodium phosphate sufficiently;
(3) 6 parts of gelatin, 8 parts of hydroxyapatites and 3 parts of succinic acid graft reaction: are added into 100 parts of water according to mass parts Mixing, in 80 DEG C of reaction 2h, obtains composite coating.
Further, the good solvent in step (3) include, one of tetrahydrofuran, ether.
Embodiment 4
A kind of preparation method of the composite coating for Bone Defect Repari, comprising the following steps:
(1) it the preparation of gelatin: chooses bone collagen and trypsase is added, it is 2 ~ 3 × 10 that reaction, which obtains molecular weight,4
(2) it the preparation of hydroxyapatite: weighs sufficiently dissolution in certain calcium nitrate addition distilled water and obtains calcium nitrate Aqueous solution, sodium phosphate is added into calcium nitrate aqueous solution, and strong stirring dissolves sodium phosphate sufficiently;
(3) according to mass parts, into 100 parts of tetrahydrofurans, 5 parts of gelatin, 8 parts of hydroxyapatite and capital graft reaction: is added The flat 7 parts of mixing of Buddhist nun, temperature are that 30 ~ 35 DEG C of reaction 3h obtain composite coating.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed New feature or any new combination, and disclose any new method or process the step of or any new combination.

Claims (10)

1. a kind of composite coating for Bone Defect Repari, including gelatin and hydroxyapatite, which is characterized in that the gelatin surface is set It is equipped with hydrophilic radical.
2. the composite coating according to claim 1 for Bone Defect Repari, which is characterized in that the hydrophilic radical be hydroxyl or Amino.
3. the composite coating according to claim 1 or 2 for Bone Defect Repari, which is characterized in that the coating contacts angle is 40 ~ 80 °, tensile strength is 30 ~ 50MPa.
4. the preparation method of the composite coating according to claim 1 for Bone Defect Repari, which is characterized in that including following Step:
(1) it the preparation of gelatin: chooses bone collagen and protease is added, it is 2 ~ 3 × 10 that reaction, which obtains molecular weight,4
(2) it the preparation of hydroxyapatite: weighs sufficiently dissolution in certain calcium nitrate addition distilled water and obtains the water-soluble of calcium nitrate Liquid, sodium phosphate is added into calcium nitrate aqueous solution, and strong stirring dissolves sodium phosphate sufficiently;
(3) graft reaction: gelatin and hydroxyapatite are sufficiently mixed by good solvent, crosslinking agent are added, in certain temperature Lower reaction obtains finished product.
5. the preparation method of the composite coating according to claim 4 for Bone Defect Repari, which is characterized in that the step (3) good solvent in includes one of water, tetrahydrofuran, ether.
6. the preparation method of the composite coating according to claim 1 for Bone Defect Repari, which is characterized in that the step (3) crosslinking agent described in is one of ethanedioic acid, succinic acid, pimelic acid.
7. the preparation method of the composite coating according to claim 6 for Bone Defect Repari, which is characterized in that the step (3) gelatin, hydroxyapatite and crosslinking agent are mixed according to 5 ~ 8:5 of mass ratio ~ 10:2 ~ 4 in.
8. the preparation method of the composite coating according to claim 6 or 7 for Bone Defect Repari, which is characterized in that the step Suddenly the reaction temperature in (3) is 75 ~ 85 DEG C.
9. the preparation method of the composite coating according to claim 1 for Bone Defect Repari, which is characterized in that the step (3) crosslinking agent described in is Geniposide, and the gelatin, hydroxyapatite and Geniposide are mixed according to 5 ~ 8:5 of mass ratio ~ 10:4 ~ 6 It closes.
10. the preparation method of the composite coating according to claim 8 for Bone Defect Repari, which is characterized in that the step (3) in, crosslinking temperature is 30 ~ 35 DEG C.
CN201811640011.0A 2018-12-29 2018-12-29 A kind of composite coating and preparation method thereof for Bone Defect Repari Pending CN109481733A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2717676C1 (en) * 2019-08-19 2020-03-25 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Bioactive coating for bone tissue recovery
RU2797279C1 (en) * 2022-07-28 2023-06-01 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Dry mixture based on hydroxyapatite for aqueous suspensions for coating on bone implants and aqueous suspension based on it

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Publication number Priority date Publication date Assignee Title
JPH08117323A (en) * 1994-10-20 1996-05-14 Baiomatsupu Kk Apatite-coated base material and method for manufacturing the same
CN101417147A (en) * 2008-12-03 2009-04-29 中国科学院上海硅酸盐研究所 Gelatin/calcium phosphate asymmetry medicine releasing coating layer and preparation method thereof
CN102397584A (en) * 2011-11-15 2012-04-04 东南大学 Medical magnesium alloy surface degradable composite protective film layer and preparation method thereof
US20140219973A1 (en) * 2011-08-23 2014-08-07 Victoria L. Boyes Composite Hydrogel-Clay Particles
CN108578252A (en) * 2018-06-05 2018-09-28 佛山皖阳生物科技有限公司 A kind of enamel surface repairs the preparation method of coating material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08117323A (en) * 1994-10-20 1996-05-14 Baiomatsupu Kk Apatite-coated base material and method for manufacturing the same
CN101417147A (en) * 2008-12-03 2009-04-29 中国科学院上海硅酸盐研究所 Gelatin/calcium phosphate asymmetry medicine releasing coating layer and preparation method thereof
US20140219973A1 (en) * 2011-08-23 2014-08-07 Victoria L. Boyes Composite Hydrogel-Clay Particles
CN102397584A (en) * 2011-11-15 2012-04-04 东南大学 Medical magnesium alloy surface degradable composite protective film layer and preparation method thereof
CN108578252A (en) * 2018-06-05 2018-09-28 佛山皖阳生物科技有限公司 A kind of enamel surface repairs the preparation method of coating material

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Title
马同江等: "《新编食品添加剂手册》", 31 December 1989, 北京:农村读物出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2717676C1 (en) * 2019-08-19 2020-03-25 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Bioactive coating for bone tissue recovery
RU2797279C1 (en) * 2022-07-28 2023-06-01 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Dry mixture based on hydroxyapatite for aqueous suspensions for coating on bone implants and aqueous suspension based on it

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Application publication date: 20190319