CN107841149B - Preparation method of hydrophilic polyphosphate amino acid copolymer composite material - Google Patents

Preparation method of hydrophilic polyphosphate amino acid copolymer composite material Download PDF

Info

Publication number
CN107841149B
CN107841149B CN201710904365.0A CN201710904365A CN107841149B CN 107841149 B CN107841149 B CN 107841149B CN 201710904365 A CN201710904365 A CN 201710904365A CN 107841149 B CN107841149 B CN 107841149B
Authority
CN
China
Prior art keywords
composite material
amino acid
acid copolymer
polyphosphate
apatite
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.)
Active
Application number
CN201710904365.0A
Other languages
Chinese (zh)
Other versions
CN107841149A (en
Inventor
吕国玉
熊熠
陈丽
井淋静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Publication of CN107841149A publication Critical patent/CN107841149A/en
Application granted granted Critical
Publication of CN107841149B publication Critical patent/CN107841149B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Polyamides (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a novel polyphosphate amino acid copolymer composite material, which is prepared from the following raw materials: apatite whisker and polyphosphate amino acid copolymer, wherein the weight of the apatite whisker is 5-50% of that of the composite material, and the polyphosphate amino acid copolymer is prepared by ring-opening polymerization of aminocaproic acid, other alpha-amino acids and cyclic phosphate. The composite material has good mechanical initial performance and biological activity, is expected to be applied to bone defect repair of spines, limbs, heads and the like caused by diseases or traumas, and has good industrial application prospect.

Description

Preparation method of hydrophilic polyphosphate amino acid copolymer composite material
Technical Field
The invention relates to a preparation method of a hydrophilic polyphosphate amino acid copolymer composite material, belonging to the field of bone repair materials.
Background
The bone tissue repair material applied to repair bone defects caused by diseases or traumas such as head, spine, limbs and the like not only needs to provide enough mechanical strength in the initial stage of implantation and does not cause stress shielding, but also has good biocompatibility as an important factor for determining whether the material can be combined with biological tissues.
However, for bone tissue repair materials, especially for load-bearing materials, it is difficult to maintain high mechanical strength without causing stress shielding, for example, the bone repair composite material disclosed in CN 101229394 a has a mechanical strength of over 800MPa, and the compressive strength of human bone is between 80MPa and 150MPa, so that stress shielding is generated, which is not favorable for normal growth of bone tissue.
Biological activity is an important criterion for judging whether a class of materials can promote bone repair, so that when designing bone repair materials, people generally prepare the materials into bone repair materials with good biological activity.
At present, the commonly used bone repair materials include polylactic acid, polyamino acid and the like. Among them, polylactic acid has good histocompatibility and biodegradability, but its strength is insufficient, and the degraded product is acidic, so that it is not favorable for growth of bone cell. The polyamino acid has a chemical structure similar to human protein, good mechanical property and no toxicity, so that the material compounded by the polyamino acid and the hydroxyapatite is widely applied to the field of bone repair. However, the contact angle of the surface of the composite material reaches more than 80 degrees, so that a better cell adhesion result cannot be obtained in the cell contact culture process, and the growth and differentiation of cells on the surface of the material are influenced.
Therefore, a bone repair material with moderate mechanical strength, no stress shielding and good biocompatibility is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a polyphosphate amino acid copolymer composite material which is prepared from the following raw materials: apatite whisker and polyphosphate amino acid copolymer, wherein the weight of the apatite whisker is 5-50% of that of the composite material, and the polyphosphate amino acid copolymer is prepared by ring-opening polymerization of aminocaproic acid, other alpha-amino acids and cyclic phosphate.
Furthermore, the weight of the apatite crystal whisker is 5-50% of the weight of the composite material, and the preferred proportion is 10-40%.
Further, Ga/P of the apatite whisker is 1.67, and the length of the apatite whisker is 10 to 100 micrometers, preferably 10 to 20 micrometers.
Further, the molar quantity of the aminocaproic acid is 75 to 95 percent of the sum of the total molar quantity of all the amino acids; preferably, the molar amount of the aminocaproic acid is 90 to 95 percent of the sum of the total molar amount of all amino acids.
Further, the mol ratio of the cyclic phosphate to the polyphosphate amino acid copolymer is 1-10%, and the preferable mol ratio is 2.5-5%.
Further, the ring phosphate is selected from five-membered ring phosphate, six-membered ring phosphate and seven-membered ring phosphate; preferably, the cyclic phosphate is a five-membered cyclic phosphate.
Further, the other alpha-amino acid is selected from any one or more than two of alanine, phenylalanine, proline, hydroxyproline, lysine, glycine, leucine, isoleucine, valine, cystine, cysteine, methionine, threonine, serine, tyrosine, tryptophan, methionine, arginine and histidine; preferably, the other alpha-amino acid is selected from the group consisting of alanine, phenylalanine, proline, hydroxyproline and lysine.
Further, the composite material is prepared by the following method: taking aminocaproic acid and other five alpha-amino acids, adding water, dehydrating and melting at 180-190 ℃ under the protection of nitrogen, heating to 200-220 ℃ for reaction for 2-3 hours, adding cyclic phosphate for reaction for 0-30 minutes, adding apatite whiskers, mixing uniformly, and cooling to obtain the polyphosphate amino acid copolymer composite material.
Further, the density of the composite material is controlled to be 1.6-2.5g/cm3。
Furthermore, the bending strength of the composite material is more than or equal to 80MPa, and the compressive strength is more than or equal to 100 MPa.
Furthermore, the contact angle of the surface of the composite material is controlled to be 40-60 degrees.
The invention also provides application of the composite material as a bone tissue repair material.
Generally, the human bone has a flexural strength of 50MPa to 120MPa and a compressive strength of 80MPa to 150 MPa. The mechanical property of the bone repair material is close to that of human bones, so that the problem of stress shielding can not be caused.
The composite material of the invention not only can provide enough mechanical strength in the initial stage, but also has good biocompatibility. Can simultaneously meet the requirements of mechanical strength and biocompatibility, is suitable for serving as a bone tissue repair material, has a cell adhesion rate higher than 110 percent relative to a blank control group, is used for repairing bone defects caused by diseases or trauma of spines, limbs, heads and the like, and has good industrial application prospect.
In addition, the amino polymer used in the invention has good initial mechanical property, is beneficial to the fixation and fusion between the material and bone tissues, the addition of phosphate improves the hydrophilicity of the surface of the material, and apatite whiskers in the composite material endow the material with biological activity, thereby playing an important role in bone tissue repair.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Detailed Description
The raw materials and equipment used in the specific embodiment of the invention are known products and are obtained by purchasing commercially available products; for example, amino acids are available from sigma.
The cell adhesion experiment adopts mesenchymal stem cells, and the determination method is implemented according to the biological evaluation of the national standard GBT.16886 medical instrument. Blank group refers to control group without any treatment.
Example 1 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000031
]Reacting for 10min after 3g, adding 45g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 98MPa, and the compressive strength is: 125 MPa. The density was 2.6g/cm3。
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 2 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after the reactor is molten, and heating to 230-235 ℃ for strip formingReacting for 1 hour under the condition of reaction, and adding cyclic phosphate [ (six elements)
Figure BDA0001423704540000032
]Reacting for 10min after 6g, adding 45g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 90MPa, compressive strength: 118 MPa. The density is 2g/cm3。
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 3 preparation of a polyphosphate amino acid copolymer composite of the invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000041
]10g of the mixture is reacted for 10min, 45g of apatite whiskers (with the particle size of 15 microns) is added, the mixture is continuously stirred for half an hour, the mixture is uniformly mixed, and the mixture is cooled to room temperature under the protection of nitrogen, so that the polyphosphate amino acid copolymer composite material is obtained.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 75MPa, compressive strength: 97 MPa. The density was 1.6g/cm3。
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 4 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000042
]Reacting for 10min after 6g, adding 45g of apatite whiskers (with the particle size of 10 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 97MPa, and the compressive strength is: 120 MPa. The density was 2.4g/cm 3.
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 5 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000051
]Reacting for 10min after 6g, adding 45g of apatite whiskers (with the particle size of 20 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 79MPa, and the compressive strength is: 102 MPa. The density was 1.8g/cm 3.
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 6 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000052
]Reacting for 10min after 6g, adding 15g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 78MPa, compressive strength: 103 MPa. The density was 2.2g/cm 3.
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 7 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000053
]10g of the mixture is reacted for 10min, then 30g of apatite whiskers (with the particle size of 15 microns) is added, the mixture is continuously stirred for half an hour, the mixture is uniformly mixed, and the mixture is cooled to room temperature under the protection of nitrogen, so that the polyphosphate amino acid copolymer composite material is obtained.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 84MPa, and the compressive strength is: 111 MPa. The density was 1.8g/cm3。
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 8 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, and adding cyclic phosphate (six-membered)
Figure BDA0001423704540000061
]Reacting for 10min after 6g, adding 60g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 72MPa, compressive strength: 110 MPa. The density was 1.6g/cm3。
The polyphosphate amino acid copolymer composite material polybasic amino acid polymer is soaked in simulated body fluid for biological activity test. After soaking for 14 days: the surface has a large amount of apatite deposited thereon.
Example 9 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000062
Reacting for 10min after 3g, adding 45g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 101MPa, compressive strength: 195 MPa. The density was 2.6g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 65 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 102 percent.
Example 10 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000071
Reacting for 10min after 6g, adding 45g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 88MPa, compressive strength: 178 MPa. The density is 2g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 52 degrees, and the cell adhesion rate of mesenchymal stem cells relative to a blank group is 110 percent.
Example 11 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000072
10g for 10min, adding 45g apatite whisker (particle size 15 μm), stirring for half an hour, mixing, and cooling under nitrogen protectionCooling to room temperature to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 68MPa, compressive strength: 155 MPa. The density was 1.6g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 47 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 117 percent.
Example 12 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000073
Reacting for 10min after 6g, adding 45g of apatite whiskers (with the particle size of 10 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 87MPa, and the compressive strength is: 170 MPa. The density was 1.9g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 54 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 109 percent.
Example 13 preparation of a polyphosphate amino acid copolymer composite of the invention
Respectively taking 122.5g, 1g, 0.9g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyprolineg. 7g and 1.5g of the mixture are added into a 250ml three-necked bottle, 100ml of distilled water is added, nitrogen is introduced for protection, the mixture is stirred and gradually heated to 180 to 190 ℃ for slow dehydration, when the reactor is in a molten state, the temperature is raised to 200 to 220 ℃ for melting and then reacting for 2 hours, then the temperature is raised to 230 to 235 ℃ for reacting for 1 hour, and five-membered ring phosphate is added
Figure BDA0001423704540000081
Reacting for 10min after 6g, adding 45g of apatite whiskers (with the particle size of 20 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 59MPa, compressive strength: 152 MPa. The density was 1.7g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 54 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 108 percent.
Example 14 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000082
Reacting for 10min after 6g, adding 15g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for bending resistanceAnd mechanical testing of compression resistance. The bending strength of the test specimen bars was: 60MPa, compressive strength: 143 MPa. The density was 1.4g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 45 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to blank groups is 120 percent.
Example 15 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000091
Reacting for 10min after 6g, adding 30g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 59MPa, compressive strength: 145 MPa. The density was 1.5g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 48 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 117 percent.
Example 16 preparation of a polyphosphate amino acid copolymer composite of the present invention
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the mixture into a 250ml three-necked flask, adding 100ml of distilled water, introducing nitrogen for protection, stirring, gradually heating to 180-190 ℃ for slow dehydration, and heating to 200-DEG C when the reactor is in a molten stateMelting at 220 deg.C, reacting for 2 hr, heating to 230-235 deg.C, reacting for 1 hr, adding five-membered ring phosphate
Figure BDA0001423704540000092
Reacting for 10min after 6g, adding 60g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 70MPa, compressive strength: 188 MPa. The density was 1.8g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 60 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 101 percent.
Comparative example 1 polyamino acid composite Material
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for 1 hour, adding 45g of apatite whiskers (with the particle size of 15 micrometers), continuously stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 110MPa, compressive strength: 210 MPa. The density is 2.8g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 80 degrees, and the cell adhesion rate of mesenchymal stem cells relative to a blank group is 96 percent. Compared with materials added with cyclic phosphate, the composite material has higher mechanical property, but the contact angle of the surface of the material is higher, so that the composite material has lower cell adhesion capability. The mechanical properties of the composite material in example 10 have reached the requirements of the support material, and at the same time, the composite material has higher cell adhesion performance, so that the composite material is more suitable for clinical application.
Comparative example 2 seven-membered ring phosphate composite
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding seven-membered ring phosphate ester
Figure BDA0001423704540000101
Reacting for 10min after 6g, adding 45g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 60MPa, compressive strength: 140 MPa. The density was 1.4g/cm3。
The contact angle of the polyphosphate amino acid copolymer composite material is 52 degrees, and the cell adhesion rate of mesenchymal stem cells relative to a blank group is 104 percent.
The performance of the composite material is reduced compared with that of a pentacyclic phosphate composite material by adopting the copolymerization of the heptatomic ring phosphate and the amino acid, but the application requirement of the material is still met.
Comparative example 3, the mechanical property of the composite material with the particle size of the apatite whisker more than 20 microns is reduced
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, respectively, adding into a 250ml three-necked flask, adding 100ml of distilled water, introducing nitrogen for protection, stirring, and gradually heating to 180 ℃longSlowly dehydrating at 190 ℃, heating to 200-220 ℃ to melt and react for 2 hours when the reactor is in a molten state, heating to 230-235 ℃ to react for 1 hour, and adding five-membered ring phosphate
Figure BDA0001423704540000102
Reacting for 10min after 6g, adding apatite whisker 45 (with the particle size of 50 microns), continuing stirring for half an hour, mixing uniformly, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 50MPa, compressive strength: 170 MPa. The density was 1.6g/cm3. The larger the particle size of the apatite whisker is, the poorer the regularity of the apatite whisker is, the poorer the dispersibility in the process of compounding the material is, and the apatite whisker is easy to agglomerate, so that the phase separation occurs locally on the material, and the mechanical property is not consistent. So that the mechanical property of the material is poorer than that of the composite material with 10-50 microns of apatite whiskers.
The contact angle of the polyphosphate amino acid copolymer composite material is 52 degrees, and the cell adhesion rate of mesenchymal stem cells relative to a blank group is 112 percent.
The composite material of embodiment 10 has the same contact angle but has a better cell adhesion rate because the poor uniformity of the composite material results in an increase in the roughness of the surface, thereby facilitating cell adhesion. Therefore, the method can be applied to clinic.
Comparative example 4, the mechanical property of the composite material with the content of apatite whiskers less than 5 percent is reduced
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for 1 hour, addingInto a five-membered ring phosphate
Figure BDA0001423704540000111
Reacting for 10min after 6g, adding 5g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite material is prepared into a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 80MPa, and the compressive strength is: 125 MPa. The density is 2g/cm3. The composite material has the characteristics close to that of polyphosphate amino acid due to less added apatite whiskers, and the density is basically consistent. Compared with the composite material added with more apatite whiskers, the mechanical property is reduced.
The contact angle of the polyphosphate amino acid copolymer composite material is 42 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 118 percent. The composite material also has good cell adhesion performance but poor mechanical properties, and therefore cannot be used as a bone repair material.
Comparative example 5, the mechanical property of the composite material with the content of apatite whiskers larger than 60g is reduced
Respectively taking 122.5g, 1g, 0.9g, 1.5g, 7g and 1.5g of aminocaproic acid, lysine, alanine, phenylalanine, glycine and hydroxyproline, adding the materials into a 250ml three-necked bottle, adding 100ml of distilled water, introducing nitrogen for protection, stirring and gradually heating to 180-190 ℃ for slow dehydration, heating to 200-220 ℃ when the reactor is in a molten state, reacting for 2 hours after melting, heating to 230-235 ℃ for reacting for 1 hour, adding five-membered cyclic phosphate ester
Figure BDA0001423704540000112
Reacting for 10min after 6g, adding 100g of apatite whiskers (the particle size is 15 microns), continuing stirring for half an hour, uniformly mixing, and cooling to room temperature under the protection of nitrogen to obtain the polyphosphate amino acid copolymer composite material.
The polyphosphate amino acid copolymer composite materialAnd preparing a standard sample strip for the mechanical test of bending resistance and compression resistance. The bending strength of the test specimen bars was: 30MPa, and the compressive strength is: 130 MPa. The density was 1.3g/cm3. The mechanical property of the composite material is obviously reduced by adding excessive apatite whiskers, because the particle size of the apatite whiskers is larger than that of amino acid, the material is subjected to phase separation by adding excessive apatite whiskers, the mechanical property of the material is close to that of the apatite whiskers, and the toughness is changed into brittleness, so that the bending and compression strength is reduced.
The contact angle of the polyphosphate amino acid copolymer composite material is 62 degrees, and the cell adhesion rate of the mesenchymal stem cells relative to the blank group is 101 percent. The cell adhesion performance of the composite material is reduced due to the increase of the content of the hydroxyapatite whisker with hydrophobicity.
In conclusion, the composite material of the invention can provide enough mechanical strength in the initial stage, the mechanical property of the material is closer to the human bone tissue, and the problem of stress shielding can not be caused; the material has good cell adhesion result, has good influence on growth and differentiation of bone tissue cells on the surface of the material, is suitable to be used as a bone tissue repair material, is used for repairing bone defects caused by diseases or trauma of spines, limbs, heads and the like, and has good industrial application prospect.

Claims (15)

1. A polyphosphate amino acid copolymer composite material is characterized in that: the composite material is prepared from the following raw materials: apatite whisker and polyphosphate amino acid copolymer, wherein the weight of the apatite whisker is 5-50% of that of the composite material, and the polyphosphate amino acid copolymer is formed by ring-opening polymerization of aminocaproic acid, other alpha-amino acids and cyclic phosphate;
Ga/P =1.67 of the apatite whisker, and the length of the apatite whisker is 10-100 microns;
the composite material is prepared by the following method: taking aminocaproic acid and other five alpha-amino acids, adding water, dehydrating and melting at 180-190 ℃ under the protection of nitrogen, heating to 200-220 ℃ for reaction for 2-3 hours, adding cyclic phosphate for reaction for 10-30 minutes, adding apatite whiskers, mixing uniformly, and cooling to obtain the polyphosphate amino acid copolymer composite material.
2. The composite material of claim 1, wherein: the weight of the apatite crystal whisker is 10 to 40 percent of the weight of the composite material.
3. The composite material of claim 2, wherein: the length of the apatite crystal whisker is 10-20 microns.
4. The composite material of claim 1, wherein: the molar quantity of the aminocaproic acid is 75 to 95 percent of the sum of the total molar quantity of all the amino acids.
5. The composite material of claim 4, wherein: the molar quantity of the aminocaproic acid is 90 to 95 percent of the sum of the total molar quantity of all the amino acids.
6. The composite material of claim 1, wherein: the mol ratio of the cyclic phosphate to the polyphosphate amino acid copolymer is 1-10%.
7. The composite material of claim 6, wherein: the mol ratio of the cyclic phosphate to the polyphosphate amino acid copolymer is 2.5-5%.
8. The composite material of claim 1, wherein: the ring phosphate is selected from five-membered ring phosphate, six-membered ring phosphate and seven-membered ring phosphate.
9. The composite material of claim 8, wherein: the cyclic phosphate is selected from five-membered cyclic phosphate.
10. The composite material of claim 1, wherein: the other alpha-amino acid is selected from any five of alanine, phenylalanine, proline, hydroxyproline, lysine, glycine, leucine, isoleucine, valine, cystine, cysteine, methionine, threonine, serine, tyrosine, tryptophan, arginine and histidine.
11. The composite material of claim 10, wherein: the other alpha-amino acids are selected from the group consisting of alanine, phenylalanine, proline, hydroxyproline, and lysine.
12. The composite material of claim 1, wherein: the density of the composite material is controlled to be 1.6-2.5g/cm3。
13. The composite material of claim 1, wherein: the bending strength of the composite material is more than or equal to 80MPa, and the compressive strength is more than or equal to 100 MPa.
14. The composite material of claim 1, wherein: the contact angle of the surface of the composite material is controlled to be 40o-60o。
15. Use of a composite material according to any one of claims 1 to 14 as a bone tissue repair material.
CN201710904365.0A 2016-09-29 2017-09-29 Preparation method of hydrophilic polyphosphate amino acid copolymer composite material Active CN107841149B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610861594 2016-09-29
CN2016108615944 2016-09-29

Publications (2)

Publication Number Publication Date
CN107841149A CN107841149A (en) 2018-03-27
CN107841149B true CN107841149B (en) 2020-10-23

Family

ID=61661878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710904365.0A Active CN107841149B (en) 2016-09-29 2017-09-29 Preparation method of hydrophilic polyphosphate amino acid copolymer composite material

Country Status (1)

Country Link
CN (1) CN107841149B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101417149A (en) * 2008-10-22 2009-04-29 四川大学 Degradable biological composite material of phosphate containing calcium and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101417149A (en) * 2008-10-22 2009-04-29 四川大学 Degradable biological composite material of phosphate containing calcium and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Unitary Bioresorbable Cage/Core Bone Graft Substitutes for Spinal Arthrodesis Coextruded from Polycaprolactone Biocomposites;Ergun, Asli; Chung, Rebecca; Ward, Daniel;;《ANNALS OF BIOMEDICAL ENGINEERING》;20111217;说明书全文 *
生物降解性聚氨基酸/聚己内酯/聚磷酸酯三嵌段共聚物的合成与胶束制备;李冬;《中国优秀硕士学位论文全文数据库，工程科技I辑》;20130528;正文部分第14页第2-3段 *

Also Published As

Publication number Publication date
CN107841149A (en) 2018-03-27

Similar Documents

Publication Publication Date Title
US20230042322A1 (en) Composite materials comprising synthetic dragline spider silk
Li et al. Degradable biocomposite of nano calcium-deficient hydroxyapatite-multi (amino acid) copolymer
Upadhyay et al. Modulation of protein adsorption and cell proliferation on polyethylene immobilized graphene oxide reinforced HDPE bionanocomposites
Hameed et al. Evaluation of polyvinyl alcohol composite membranes containing collagen and bone particles
CN106860916B (en) GO/nHA/collagen composite bone repair material and preparation method thereof
Cimpean et al. Osteoblast cell behavior on the new beta-type Ti–25Ta–25Nb alloy
Chen et al. Biomineralized hydrogel with enhanced toughness by chemical bonding of alkaline phosphatase and vinylphosphonic acid in collagen framework
Luo et al. Preparation and properties of nanometer silk fibroin peptide/polyvinyl alcohol blend films for cell growth
CN110893249A (en) Pearl powder and polyamino acid composite bone repair material with osteogenic activity and preparation method and application thereof
CN101698117B (en) Bone-repairing composite material and method for preparing the same
CN105536054B (en) A kind of composite material of bio-vitric/amino acid polymer and its application
CN107841149B (en) Preparation method of hydrophilic polyphosphate amino acid copolymer composite material
Mohammed et al. The nanomechanical characterization and tensile test of polymer nanocomposites for bioimplants
Baheiraei et al. Investigation of magnesium incorporation within gelatin/calcium phosphate nanocomposite scaffold for bone tissue engineering
He et al. Novel hydroxyapatite/tussah silk fibroin/chitosan bone-like nanocomposites
Ghasemi et al. Evaluation of the effects of zein incorporation on physical, mechanical, and biological properties of polyhydroxybutyrate electrospun scaffold for bone tissue engineering applications
Kulkarni et al. Self-assembly of trifunctional tripeptides to form neural scaffolds
CN108219360B (en) Medical polyether-ether-ketone composite material and preparation method thereof
CN111388752B (en) PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof
Kashan et al. Effect of Multi-Walled Carbon Nanotube on the Microstructure, Physical and Mechanical Properties of ZrO2–CaO/Poly (methyl methacrylate) Biocomposite for Bone Reconstruction Application
CN105597147B (en) A kind of preparation method of bio-vitric/amino acid polymer composite material
Ran et al. Comparisons between gelatin-tussah silk fibroin/hydroxyapatite and gelatin-Bombyx mori silk fibroin/hydroxyapatite nano-composites for bone tissue engineering
Lu et al. Silk‐Fabric Reinforced Silk for Artificial Bones
Won et al. Gelatin-apatite bone mimetic co-precipitates incorporated within biopolymer matrix to improve mechanical and biological properties useful for hard tissue repair
Al-Allaq et al. The bio-composites (Hydroxyapatite/High-density polyethylene) materials rein-forced with Multi-walled carbon nanotubes for bone tissue repair

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
GR01 Patent grant
GR01 Patent grant