CN108404217B - Method for rapidly preparing large-size calcium phosphate/chitosan organic-inorganic hybrid material by one-step method - Google Patents

Method for rapidly preparing large-size calcium phosphate/chitosan organic-inorganic hybrid material by one-step method Download PDF

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CN108404217B
CN108404217B CN201810576143.5A CN201810576143A CN108404217B CN 108404217 B CN108404217 B CN 108404217B CN 201810576143 A CN201810576143 A CN 201810576143A CN 108404217 B CN108404217 B CN 108404217B
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chitosan
calcium phosphate
organic
calcium
solution
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CN108404217A (en
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王征科
方雯
杨玲
胡巧玲
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Zhejiang University ZJU
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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
    • A61L27/40—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
    • 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 method for rapidly preparing a large-size calcium phosphate/chitosan organic-inorganic hybrid material by a one-step method, which comprises the following steps: calcium acetate powder was used as the source of calcium ions, added to the acetic acid solution of chitosan, and urea was added until a clear homogeneous solution was formed. Injecting the homogeneous solution into a mold, and then soaking in NaOH and Na3PO4And (3) in a mixed coagulation bath, demolding, cleaning and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material. The invention adopts a one-step preparation process, combines a coagulating bath and a converting bath into a whole, completes the in-situ precipitation of calcium phosphate crystals in the gel forming process, and has simple and quick preparation process. The prepared composite material successfully maintains the original three-dimensional ordered structure characteristic of the chitosan gel, and simultaneously successfully introduces the calcium phosphate inorganic substance component, has adjustable organic/inorganic content, can prepare composite materials with different mineral contents, and meets the requirements of the bone repair field on calcium source, structure and performance.

Description

Method for rapidly preparing large-size calcium phosphate/chitosan organic-inorganic hybrid material by one-step method
Technical Field
The invention relates to a method for rapidly preparing a large-size calcium phosphate/chitosan organic-inorganic hybrid material by a one-step method.
Background
Biominerals are important components of living bodies, and natural biominerals are almost all organic-inorganic composite materials formed by self-assembly and rarely consist of pure inorganic minerals such as bones, teeth, shells, pearls and the like. The composite materials from the nature have precise structures and excellent performance, and almost all excellent biominerals adopt a strategy of regulating inorganic phase growth by organic molecules, so that the research on the generation process of organic-inorganic composites in the nature and the construction of organic-inorganic composite bionic materials under the action of an organic template framework have important significance.
The calcium phosphate cement has good biocompatibility and osteogenesis activity, can be self-cured and molded at room temperature, has an isothermal curing process, and has been successfully applied to the repair and replacement of hard tissues in clinical medicine. The chitosan is a natural high molecular polysaccharide, has the advantages of good biocompatibility, no immunogenicity, biodegradability and the like, and is widely applied in the field of biomedicine. The calcium phosphate/chitosan system is one of the key concerns in the research of organic and inorganic composite materials. The chitosan hydrogel with ordered structure and excellent performance can be simply, conveniently and rapidly prepared by an in-situ precipitation method, and the calcium phosphate can be introduced by combining with inorganic in-situ mineralization. The calcium phosphate can be transformed into hydroxyapatite under the physiological condition of human body, has a similar composition structure with natural bone apatite, can participate in metabolism after being implanted into the human body, and has good bone conductivity and bone inductivity. Therefore, the one-step method for rapidly preparing the large-size calcium phosphate/chitosan composite material has good practical application value in the field of bone tissue engineering.
Disclosure of Invention
The invention aims to provide a method for rapidly preparing a large-size calcium phosphate/chitosan organic-inorganic material by one-step process aiming at the defects of the prior art.
The invention relates to a method for rapidly preparing a large-size calcium phosphate/chitosan organic-inorganic material by a one-step method, which comprises the following steps:
1) weighing chitosan with the mass viscosity-average molecular weight of 1-120 ten thousand and the deacetylation degree of 60-95% as a solute, taking an acetic acid aqueous solution with the volume fraction of 2-20% as a solvent, stirring until the chitosan is completely dissolved, and preparing a chitosan solution A with the mass viscosity-average molecular weight of 2-10 wt.%;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B; the calcium acetate powder is calcium phosphate (Ca) corresponding to calcium ion in Chitosan (CS) mass3(PO4)2]Measured by mass ratio of theoretical value, such that m (CS) m [ Ca ]3(PO4)2]60:40-4: 96; adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: injecting the solution C into a single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, wherein the NaOH concentration is 2-10 wt.%, c (NaOH): c (Na)3PO4) 1:1-3: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The invention adopts a one-step preparation process, combines the coagulating bath and the transforming bath into a whole, completes the in-situ precipitation of the calcium phosphate crystal in the gel forming process, and has simple and quick preparation process. The prepared large-size chitosan-calcium phosphate composite material successfully maintains the original three-dimensional ordered structure characteristic of chitosan gel, and simultaneously successfully introduces calcium phosphate inorganic matter components, and the organic/inorganic content ratio of the composite material can be regulated and controlled by simply changing the feed ratio, the coagulation bath condition and the like, so that composite materials with different mineral contents are prepared, the requirements of the bone repair field on calcium source, structure and performance are met, and particularly the composite material with high mineral content can be prepared by the method.
The invention can well solve the problem that inorganic matters are dispersed unevenly in organic matters and are easy to settle by introducing the urea, so that the inorganic matters can be uniformly distributed among the organic matters, and the organic/inorganic hybrid material with high inorganic matter content can be obtained. In addition, the method can greatly shorten the mineralization time of inorganic substances so as to shorten the preparation period, the traditional preparation method of the organic/inorganic hybrid materials usually needs more than one week, and the method can obtain mineralized products within 6 hours.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 1 ten thousand and the deacetylation degree of 60%) and adding the chitosan into a 100mL beaker, adding 9mL of 2% acetic acid aqueous solution by volume fraction, and uniformly stirring to obtain 10 wt.% of chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 4: 96. Adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: injecting the solution C into a single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, wherein NaOH concentration is 2 wt.%, c (NaOH): c (Na)3PO4) 1: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The inorganic content of the large-size (10cm multiplied by 2cm) calcium phosphate/chitosan organic-inorganic hybrid material prepared by the embodiment is 94.9%.
Example 2:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 20 ten thousand and the deacetylation degree of 70%) and adding the chitosan into a 100mL beaker, adding 11.5mL of acetic acid aqueous solution with the volume fraction of 5%, and uniformly stirring to obtain 8 wt.% of chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 20: 80. Adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: mixing the solution CInjecting into single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, where NaOH concentration is 4 wt.%, c (NaOH): c (Na)3PO4) 1: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The inorganic content of the large-size (10cm multiplied by 2cm) calcium phosphate/chitosan organic-inorganic hybrid material prepared by the embodiment is 79.1 percent.
Example 3:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 50 ten thousand and the deacetylation degree of 80%) and adding the chitosan into a 100mL beaker, then adding 19mL of acetic acid aqueous solution with the volume fraction of 10%, and uniformly stirring to obtain 5 wt.% of chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 25: 75. Adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: injecting the solution C into a single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, wherein NaOH concentration is 5 wt.%, c (NaOH): c (Na)3PO4) Is 2: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The inorganic content of the large-size (10cm multiplied by 2cm) calcium phosphate/chitosan organic-inorganic hybrid material prepared by the embodiment is 73.3 percent.
Example 4:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 100 ten thousand and the deacetylation degree of 90%) and adding the chitosan into a 100mL beaker, adding 24mL of acetic acid aqueous solution with the volume fraction of 15%, and uniformly stirring to obtain 4 wt.% of chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 40: 60. Adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: injecting the solution C into a single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, where NaOH concentration is 8 wt.%, c (NaOH): c (Na)3PO4) Is 2: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The inorganic content of the large-size calcium phosphate/chitosan organic-inorganic hybrid material prepared by the embodiment is 59.3%.
Example 5:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 120 ten thousand and the deacetylation degree of 95%) and adding the chitosan into a 100mL beaker, adding 49mL of 20% volume fraction acetic acid aqueous solution, and uniformly stirring to obtain 2 wt.% chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 60: 40. Adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: solution C was poured into a single-opening mold and immersedNaOH、Na3PO4Mixed coagulation bath, where NaOH concentration is 10 wt.%, c (NaOH): c (Na)3PO4) Is 3: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel with deionized water to be neutral, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material.
The inorganic content of the large-size calcium phosphate/chitosan organic-inorganic hybrid material prepared by the method is 39.2 percent.
Example 6:
1) weighing 1g of chitosan (with the viscosity-average molecular weight of 100 ten thousand and the deacetylation degree of 90%) and adding the chitosan into a 100mL beaker, adding 24mL of acetic acid aqueous solution with the volume fraction of 15%, and uniformly stirring to obtain 4 wt.% of chitosan solution A;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solution B. The added amount of calcium phosphate [ Ca ] is corresponding to the mass of Chitosan (CS) and calcium ions3(PO4)2]Mass ratio of m (CS) m [ Ca ]3(PO4)2]Is 40: 60. Flocculent precipitate is formed in the mixed solution B, and under the condition of not adding urea, the system always presents a turbid gel state, and the requirement of in-situ mineralization in a coagulation bath cannot be met, so that the subsequent operation cannot be carried out.
It can be seen that under the condition of not adding micromolecular urea to regulate, large-size calcium phosphate/chitosan organic-inorganic hybrid material can not be prepared.

Claims (1)

1. A method for rapidly preparing a large-size calcium phosphate/chitosan organic-inorganic hybrid material by a one-step method is characterized by comprising the following steps:
1) weighing chitosan with the mass viscosity-average molecular weight of 1-120 ten thousand and the deacetylation degree of 60-95% as a solute, taking an acetic acid aqueous solution with the volume fraction of 2-20% as a solvent, stirring until the chitosan is completely dissolved, and preparing a chitosan solution A with the mass viscosity-average molecular weight of 2-10 wt.%;
2) weighing a certain mass of calcium acetate powder, and adding the calcium acetate powder into the chitosan solution A to form a mixture stock solutionB, the addition amount of the calcium acetate powder is calcium phosphate [ Ca ] corresponding to the mass of the Chitosan (CS) and calcium ions3(PO4)2]The mass ratio of m (CS) to m [ Ca ] is measured3(PO4)2]Is 25:75-4: 96; adding a certain amount of urea till the light transmittance of the mixed solution measured by a WGT-S haze meter is more than 90 percent to obtain a homogeneous mixed solution C;
3) the composite hydrogel is prepared by a one-step method, which comprises the following specific steps: injecting the solution C into a single-opening mold, and soaking in NaOH and Na3PO4Mixed coagulation bath, wherein the NaOH concentration is 2-10 wt.%, c (NaOH): c (Na)3PO4) 1:1-3: 1;
4) and demolding the obtained chitosan-based composite gel, repeatedly washing the chitosan-based composite gel to be neutral by using deionized water, and drying to obtain the large-size calcium phosphate/chitosan organic-inorganic hybrid material, wherein the mass fraction of total calcium phosphate of the organic-inorganic hybrid material is as high as 73.3% -95%.
CN201810576143.5A 2018-06-06 2018-06-06 Method for rapidly preparing large-size calcium phosphate/chitosan organic-inorganic hybrid material by one-step method Expired - Fee Related CN108404217B (en)

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