CN105536054A - Composite material of bioglass/amino acid polymer and application thereof - Google Patents
Composite material of bioglass/amino acid polymer and application thereof Download PDFInfo
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- CN105536054A CN105536054A CN201511033147.1A CN201511033147A CN105536054A CN 105536054 A CN105536054 A CN 105536054A CN 201511033147 A CN201511033147 A CN 201511033147A CN 105536054 A CN105536054 A CN 105536054A
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- 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
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses a composite material of bioglass/amino acid polymer. The composite material is formed by mixing bioglass and amino acid polymer, wherein the weight percentage of the bioglass is 17-55%. According to the composite material, enough mechanical strength can be provided in the early stage, the composite material can be quickly degraded in the later stage, and requirements of mechanical strength and degradability can be met at the same time. The composite material is suitable for serving as a bone tissue repair material, can be used for repairing bone defects, caused by lesion or injuries, of the spine, four limbs, the head and the like, and is good in industrial application prospect.
Description
Technical field
The present invention relates to a kind of composite and application thereof of bio-vitric/amino acid polymer.
Background technology
Osseous tissue renovating material, when being applied to the bone defect healing that spinal column, extremity, head etc. cause because of pathological changes or wound, require that the initial stage implanting provides sufficiently high mechanical strength on the one hand, simultaneously, requiring again on the other hand can fast degradation in the osseous tissue healing later stage, the unpredictable risk brought to avoid changes in material properties.
But, for osseous tissue renovating material, keep higher mechanical strength and fast degradation to be the contradiction mutually restricted for a pair, such as, the bone-repairing composite material of Chinese patent CN101716380A, can fast degradation, but mechanical strength is very low, comprcssive strength is at below 17MPa; And the bone renovating material of Chinese patent CN104324415A, sufficiently high mechanical strength can be provided, but be difficult to degraded; Visible, existing bone renovating material is difficult to the requirement simultaneously meeting above-mentioned two aspects usually, and effect when causing it to be applied to bone defect healing is also poor.
In order to overcome the defect of prior art, needing to invent a kind of new material, the requirement of mechanical strength and degradation property two aspect can be met simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of composite of bio-vitric/amino acid polymer.
The composite of a kind of bio-vitric/amino acid polymer provided by the invention, it is mixed by bio-vitric and amino acid polymer; Wherein, the percentage by weight of described bio-vitric is 17% ~ 55%.
Further, the percentage by weight of described bio-vitric is 34% ~ 55%.
Further, the particle diameter of described bio-vitric is 10 microns ~ 30 microns.
Further, the particle diameter of described bio-vitric is 25 microns ~ 30 microns.
Further, described amino acid polymer is formed by the polymerizable raw material of following mol ratio: episilon amino caproic acid 75% ~ 95%, other a-amino acid 5% ~ 25%; Preferably, described amino acid polymer is formed by the polymerizable raw material of following mol ratio: episilon amino caproic acid 90% ~ 95%, other a-amino acid 5% ~ 10%.
Further, described composite is prepared from by following methods: get episilon amino caproic acid and other a-amino acid, add water, under nitrogen protection, at 150 DEG C ~ 160 DEG C after dehydration, be warming up to 200 DEG C ~ 220 DEG C reactions 2 hours ~ 3 hours, be warming up to 230 DEG C ~ 235 DEG C reactions again after 1 hour ~ 2 hours, add bio-vitric, mixing, cooling, obtains the composite of bio-vitric/amino acid polymer;
The mol ratio of episilon amino caproic acid and other a-amino acid is: episilon amino caproic acid 75% ~ 95%, other a-amino acid 5% ~ 25%.
Further, the mol ratio of episilon amino caproic acid and other a-amino acid is: episilon amino caproic acid 90% ~ 95%, other a-amino acid 5% ~ 10%.
Further, other described a-amino acid be selected from alanine, phenylalanine, proline, hydroxyproline, lysine, glycine, leucine, isoleucine, valine, cystine, cysteine, methionine, threonine, serine, tyrosine, tryptophan, methionine, arginine, histidine any one or two or more; Preferably, other described a-amino acid is made up of alanine, phenylalanine, proline, hydroxyproline and lysine.
Further, when described composite soaks 4 weeks in simulated body fluid, the comprcssive strength of composite is more than 70MPa.
Present invention also offers the application of above-mentioned composite as osseous tissue renovating material.
Usually, the healing time of osseous tissue is 12 weeks ~ 24 weeks, if repair materials can not major part be degraded (degraded more than 85%) within this time, repair materials can be wrapped, and is more difficult to degraded, affects the healing of osseous tissue.Composite of the present invention soaks 12 weeks ~ 24 weeks in simulated body fluid, composite degradation more than 85%; Preferably, composite of the present invention soaks 12 weeks ~ 16 weeks in simulated body fluid, and composite degradation is complete.
The amino acid starting material such as episilon amino caproic acid, alanine that the present invention uses, there is good biological activity and biocompatibility, be conducive to tissue and the interaction between cell and material, its catabolite is close to neutral oligopeptide or aminoacid micromolecule, or being degraded to carbon dioxide and water discharge further, safety is very high.
Composite of the present invention, both enough mechanical strengths can be provided in the early stage, again can at later stage fast degradation, the requirement of mechanical strength and degradation property two aspect can be met simultaneously, be suitable as osseous tissue renovating material, for the bone defect healing that spinal column, extremity, head etc. cause because of pathological changes or wound, there is good industrial application prospect.
Obviously, according to foregoing of the present invention, according to ordinary technical knowledge and the customary means of this area, not departing under the present invention's above-mentioned basic fundamental thought prerequisite, the amendment of other various ways, replacement or change can also be made.
The detailed description of the invention of form by the following examples, is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.All technology realized based on foregoing of the present invention all belong to scope of the present invention.
Detailed description of the invention
The raw material used in the specific embodiment of the invention, equipment are known product, obtain by buying commercially available prod; Such as, bio-vitric is bought from Gao An bio tech ltd, Shanghai.
Is simulated body fluid prepared according to the method in Publication about Document: T.Kokubo, H.Takadama.HowusefulisSBFinpredictinginvivobonebioactivi ty? Biomaterials, 2006; 27 (15): 2907-15.
The composite of embodiment 1, preparation bio-vitric/amino acid polymer of the present invention
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C ~ 160 DEG C and slowly dewaters, when being solid in reactor, be warming up to 200 DEG C ~ 220 DEG C and make after its melting reaction 2 hours, then react 1 hour under being warming up to 230 DEG C ~ 235 DEG C conditions, generate amino acid polymer 107g, add bio-vitric 56g (particle diameter 30 microns) again, continue to stir half an hour, mixing, room temperature is cooled under nitrogen protection, obtain bio-vitric/amino acid polymer composite.
This bio-vitric/amino acid polymer composite batten is carried out in simulated body fluid degraded and mechanics loss test, with same ratio polybasic amino acids polymer for contrast.
Composite of the present invention, soaks 4 weeks, and weightless 26%, recording the comprcssive strength residual value testing all bars is 81MPa, and soak 16 weeks, material is degradable; Composite of the present invention, both can provide enough mechanical strengths in the early stage, at later stage fast degradation, can meet the requirement of mechanical strength and degradation property two aspect again simultaneously.
Control sample, soaks 4 weeks, and degraded 11%, comprcssive strength residual value 92Mpa, soaks 16 weeks, and degraded 19%, can not meet the requirement of bone renovating material to degradation property.
The composite of embodiment 2, preparation bio-vitric/amino acid polymer of the present invention
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C ~ 160 DEG C and slowly dewaters, when being solid in reactor, be warming up to 200 DEG C ~ 220 DEG C and make after its melting reaction 2 hours, then react 1 hour under being warming up to 230 DEG C ~ 235 DEG C conditions, generate amino acid polymer 107g, add bio-vitric 23.1g (particle diameter 30 microns) again, continue to stir half an hour, mixing, room temperature is cooled under nitrogen protection, obtain bio-vitric/amino acid polymer composite.
This bio-vitric/amino acid polymer composite batten is carried out in simulated body fluid degraded and mechanics loss test.
Composite of the present invention, soaks 4 weeks, and weightless 17%, recording the comprcssive strength residual value testing all bars is 90MPa, soaks 24 weeks, material degradation 85%; Composite of the present invention, both can provide enough mechanical strengths in the early stage, at later stage fast degradation, can meet the requirement of mechanical strength and degradation property two aspect again simultaneously.
The composite of embodiment 3, preparation bio-vitric/amino acid polymer of the present invention
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C ~ 160 DEG C and slowly dewaters, when being solid in reactor, be warming up to 200 DEG C ~ 220 DEG C and make after its melting reaction 2 hours, then react 1 hour under being warming up to 230 DEG C ~ 235 DEG C conditions, generate amino acid polymer 107g, add bio-vitric 130.9g (particle diameter 30 microns) again, continue to stir half an hour, mixing, room temperature is cooled under nitrogen protection, obtain bio-vitric/amino acid polymer composite.
This bio-vitric/amino acid polymer composite batten is carried out in simulated body fluid degraded and mechanics loss test.
Composite of the present invention, soaks 4 weeks, and weightless 32%, recording the comprcssive strength residual value testing all bars is 71MPa, and soak 12 weeks, material is degradable; Composite of the present invention, both can provide enough mechanical strengths in the early stage, at later stage fast degradation, can meet the requirement of mechanical strength and degradation property two aspect again simultaneously.
The bio-vitric that comparative example 1, particle diameter are greater than 30 microns causes composite avalanche in 4 weeks
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C ~ 160 DEG C and slowly dewaters, when being solid in reactor, heat up, and maintain the temperature at 200 DEG C-220 DEG C and to make after its melting reaction 2 hours, then heat up, and react 1 hour under maintaining the temperature at 230 DEG C of-235 DEG C of conditions, generate amino acid polymer 107g, add bio-vitric 130.9g (particle diameter 50 microns) again, continue to stir half an hour, mixing, room temperature is cooled under nitrogen protection, obtain the material of comparative example 1.
The material batten of this comparative example 1 is carried out in simulated body fluid degraded and mechanics loss test, soak 4 weeks, weightless 44%, soak sample cracking, the requirement as bone renovating material application can not be met.
The bio-vitric that comparative example 2, particle diameter are less than 10 microns causes material degradation speed to slow down
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C-160 DEG C and slowly dewaters, when being solid in reactor, heat up, and maintain the temperature at 200 DEG C-220 DEG C and to make after its melting reaction 2 hours, then heat up, and react 1 hour under maintaining the temperature at 230 DEG C of-235 DEG C of conditions, generate amino acid polymer 107g, add bio-vitric 130.9g (particle diameter 1-5 micron) again, continue to react half an hour.Be cooled to room temperature under nitrogen protection, obtain the material of comparative example 2.
The material batten of this comparative example 2 is carried out in simulated body fluid degraded and mechanics loss test, after soaking 4 weeks, weightless 21%, after soaking 24 weeks, weightless 67%, degraded not exclusively, can not meet the requirement of bone renovating material later stage fast degradation.
Comparative example 3, to contrast with Chinese patent CN104324415A
According to the method in Chinese patent CN104324415 embodiment, prepare modified apatite/amino acid polymer composite, in contrast sample.
This control sample batten is carried out in simulated body fluid degraded and mechanics loss test, after soaking 4 weeks, weightlessness is only after 4%, 12 weeks, and weightlessness 6%, is difficult to degraded, can not meets the requirement of bone renovating material later stage fast degradation.
Comparative example 4, bio-vitric content are less than 15%
Get episilon amino caproic acid respectively, alanine, phenylalanine, proline, hydroxyproline, the each 122.5g of lysine, 0.9g, 0.8g, 1.2g, 4g, 1.5g, add in 250ml three-necked bottle, add 70ml distilled water, logical nitrogen protection, stirring is progressively warming up to 150 DEG C-160 DEG C and slowly dewaters, when being solid in reactor, heat up, and maintain the temperature at 200 DEG C-220 DEG C and to make after its melting reaction 2 hours, then heat up, and react 1 hour under maintaining the temperature at 230 DEG C of-235 DEG C of conditions, generate amino acid polymer 107g, add bio-vitric 15g (particle diameter 30 microns) again, continue to react half an hour.Be cooled to room temperature under nitrogen protection, obtain the material of comparative example 4.
The material batten of this comparative example 4 is carried out in simulated body fluid degraded and mechanics loss test, after soaking 4 weeks, weightless 8%, recording the comprcssive strength residual value testing all bars is 88MPa, after soaking 24 weeks, material weightlessness is 36%, and degraded not exclusively, can not meet the requirement of bone renovating material later stage fast degradation.
In sum, composite of the present invention, both enough mechanical strengths can be provided in the early stage, again can at later stage fast degradation, the requirement of mechanical strength and degradation property two aspect can be met simultaneously, be suitable as osseous tissue renovating material, for the bone defect healing that spinal column, extremity, head etc. cause because of pathological changes or wound, there is good industrial application prospect.
Claims (10)
1. a composite for bio-vitric/amino acid polymer, is characterized in that: it is prepared from by bio-vitric and amino acid polymer; Wherein, the percentage by weight of described bio-vitric is 17% ~ 55%.
2. composite according to claim 1, is characterized in that: the percentage by weight of described bio-vitric is 34% ~ 55%.
3. composite according to claim 1, is characterized in that: the particle diameter of described bio-vitric is 10 microns ~ 30 microns.
4. composite according to claim 3, is characterized in that: the particle diameter of described bio-vitric is 25 microns ~ 30 microns.
5. composite according to claim 1, is characterized in that: described amino acid polymer is formed by the polymerizable raw material of following mol ratio: episilon amino caproic acid 75% ~ 95%, other a-amino acid 5% ~ 25%; Preferably, described amino acid polymer is formed by the polymerizable raw material of following mol ratio: episilon amino caproic acid 90% ~ 95%, other a-amino acid 5% ~ 10%.
6. composite according to claim 1, it is characterized in that: described composite is prepared from by following methods: get episilon amino caproic acid and other a-amino acid, add water, under nitrogen protection, at 150 DEG C ~ 160 DEG C after dehydration, be warming up to 200 DEG C ~ 220 DEG C reactions 2 hours ~ 3 hours, be warming up to 230 DEG C ~ 235 DEG C reactions again after 1 hour ~ 2 hours, add bio-vitric, mixing, cooling, obtains the composite of bio-vitric/amino acid polymer;
The mol ratio of episilon amino caproic acid and other a-amino acid is: episilon amino caproic acid 75% ~ 95%, other a-amino acid 5% ~ 25%.
7. composite according to claim 6, is characterized in that: the mol ratio of episilon amino caproic acid and other a-amino acid is: episilon amino caproic acid 90% ~ 95%, other a-amino acid 5% ~ 10%.
8. the composite according to claim 5 ~ 7 any one, is characterized in that: other described a-amino acid be selected from alanine, phenylalanine, proline, hydroxyproline, lysine, glycine, leucine, isoleucine, valine, cystine, cysteine, methionine, threonine, serine, tyrosine, tryptophan, methionine, arginine, histidine any one or two or more; Preferably, other described a-amino acid is made up of alanine, phenylalanine, proline, hydroxyproline and lysine.
9. composite according to claim 1, is characterized in that: when described composite soaks 4 weeks in simulated body fluid, and the comprcssive strength of composite is more than 70MPa.
10. the composite described in claim 1 ~ 9 any one is as the application of osseous tissue renovating material.
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Cited By (4)
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| CN111110910A (en) * | 2019-12-31 | 2020-05-08 | 中鼎凯瑞科技成都有限公司 | Zeolite polyamino acid composite medical material with hemostatic function and preparation method and application thereof |
| CN111407927A (en) * | 2020-03-31 | 2020-07-14 | 四川大学 | Clinically moldable magnesium silicate/polyamino acid composite material and application thereof in preparation of bone repair material |
| CN111437440A (en) * | 2020-04-02 | 2020-07-24 | 杭州鹿扬科技有限公司 | Controllable degradable bone implantation composite material and preparation method thereof |
| CN113754556A (en) * | 2021-09-29 | 2021-12-07 | 中国科学院过程工程研究所 | Glass based on amino acid, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111110910A (en) * | 2019-12-31 | 2020-05-08 | 中鼎凯瑞科技成都有限公司 | Zeolite polyamino acid composite medical material with hemostatic function and preparation method and application thereof |
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| CN113754556A (en) * | 2021-09-29 | 2021-12-07 | 中国科学院过程工程研究所 | Glass based on amino acid, preparation method and application thereof |
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| CN105536054B (en) | 2019-03-12 |
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