CN101693021A - Organic/inorganic hybridized microcapsule prepared in biomimetic way by simulated body fluid method and preparation method thereof - Google Patents

Organic/inorganic hybridized microcapsule prepared in biomimetic way by simulated body fluid method and preparation method thereof Download PDF

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CN101693021A
CN101693021A CN200910070808A CN200910070808A CN101693021A CN 101693021 A CN101693021 A CN 101693021A CN 200910070808 A CN200910070808 A CN 200910070808A CN 200910070808 A CN200910070808 A CN 200910070808A CN 101693021 A CN101693021 A CN 101693021A
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body fluid
simulated body
chitosan
microcapsule
solution
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姜忠义
张蕾
石家福
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Tianjin University
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Tianjin University
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Abstract

The invention relates to an organic/ inorganic hybridized microcapsule prepared in biomimetic way by simulated body fluid method and a preparation method thereof. In simulated body fluid, the hybridized microcapsule is prepared by adopting sodium alga acid and chitosan as raw materials, wherein the mass percent of sodium alga acid solution is 1.0%-3.0% and the mass percent of chitosan solution is 0.5%-1.2%. The simulated body fluid solution of the sodium alga acid reacts with the simulated body fluid solution of the chitosan, which contains Ca 2+ ions, to produce a hydroxyapatite biomimetic-mineralized polysaccharose microcapsule, placing in the chitosan solution and then washing with water. The invention has the advantages of simple and convenient operation and gentle reaction condition, uniform prepared hybridized microsphere, good stability, and excellent repeatability.

Description

Biomimetic way by simulated body fluid method prepares organic/inorganic hybridized microcapsule and preparation method thereof
Technical field:
The present invention relates to the preparation of composite, particularly a kind of biomimetic way by simulated body fluid method prepares organic/inorganic hybridized microcapsule and preparation method thereof, is specially the method that biomimetic way by simulated body fluid method prepares organic-inorganic hybrid material.
Background technology:
Organic/inorganic hybridized microcapsule can be used as a kind of multifunctional material because it has suitable hydrophilic, controlled mass transfer characteristic and good physicochemical properties, is widely used in medicine embedding, immobilized enzyme and cell, cosmetics aspect such as guarantee the quality.At present, the preparation method of organic inorganic hybridization carrier mainly contains: insertion, situ aggregation method, self-assembly method and sol-gal process etc.Insertion technology is simple, and raw material sources enrich cheap, owing to the lamella inorganic matter only is in nanoscale on unidimensional thickness direction, easily disperse simultaneously, but the processing before the lamella thing intercalation is relatively more difficult.Situ aggregation method is exactly with behind nanoparticle and the monomer mix homogeneously, trigger monomer polymerization under proper condition.But monomer such as high-energy radiation, plasma initiating method reaction condition is violent, makes the hybridization carrier scope of application limited.Self-assembly method is that the charged substrate that will handle successively immerses in the polyelectrolyte solution and inorganic matter micelle particle solution of previously prepared oppositely charged, after a while because the electrostatic attraction effect of opposite charges, polyelectrolyte, inorganic nano-particle will be assembled on the substrate successively, repeat this process and can obtain multilayer complex films, the thickness of film is linear with the increase of the number of plies to increase controllable thickness.At present, sol-gal process is modal method, it can be avoided, and high-temperature process is caused to be separated, allow mix a large amount of Organic substance and inorganic matter, the high-purity that is easy to get and high material uniformly, but predecessor costs an arm and a leg and is poisonous, and acid (or alkali) catalyst has also limited its extensive use.
Simulated body fluid method is a kind of of sol-gal process, prepares organic/inorganic hybridized microcapsule in the environment similar to body fluid.Utilize in the animal body that dissolved micro-calcium can form hard inorganic matters such as skeleton, fingernail, tooth in the body fluid.Studies show that, make up the nanostructured inorganic layer, promptly promote and regulate and control the precipitation of inorganic carbonate calcium by the electrostatic attraction effect by certain Organic substance by in the simulated body fluid environment, utilizing biomineralization.Some natural or synthetic Organic substance, as silicatein, polylysine, polyamine class etc. can be under room temperature fire neutral PH condition the rapid polymerization of regulation and control silicon dioxide and calcium carbonate.
Summary of the invention:
The object of the present invention is to provide a kind of biomimetic way by simulated body fluid method to prepare organic/inorganic hybridized microcapsule and preparation method thereof, the preparation condition gentleness has been avoided the use of acid base catalysator, organic solvent, and granular size is controlled, the scope of application is wider.This method prepares hybrid microspheres size homogeneous, good stability, favorable repeatability.
It is in simulated body fluid that a kind of biomimetic way by simulated body fluid method provided by the invention prepares organic/inorganic hybridized microcapsule, with sodium alginate and chitosan is the feedstock production hybridized microcapsule, the mass fraction of sodium alginate soln is 1.0%-3.0%, the mass fraction 0.5%-1.2% of chitosan solution, concrete technology: the simulated body fluid solution of sodium alginate and the simulated body fluid of chitosan contain Ca 2+The ion solution reaction generates the polysaccharide microcapsule of hydroxyapatite biomimetic mineralization, after placing in chitosan solution, uses water rinse.
The preparation method of the organic/inorganic hybridized microcapsule of a kind of biomimetic way by simulated body fluid method preparation provided by the invention may further comprise the steps:
1) preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 30~120.0mmol/L Ca 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-
2) preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 50~200.0mmol/L HPO 4 2-, 0.5mmol/L SO 4 2-
3) sodium alginate is dissolved in the simulated body fluid (II), being made into mass fraction is the 1.0%-3.0% sodium alginate soln.
4) chitosan is dissolved in the simulated body fluid (I), is made into mass fraction 0.5%-1.2% and contains Ca 2+Ionic chitosan solution.
5) be under 7 the condition at room temperature, sodium alginate soln is added in the chitosan solution, stir, obtain the polysaccharide microcapsule droplet that diameter is about 2mm hydroxyapatite biomimetic mineralization with pH.
6) the microcapsule droplet is preserved in chitosan solution after 20-50 minute and is taken out, and is placed on rinsing in the water then.
The invention provides organic/inorganic hybridized microcapsule of biomimetic way by simulated body fluid method preparation and preparation method thereof.Organic/inorganic hybridized microcapsule can solve the problem that pure organic microcapsule swelling is leaked effectively in conjunction with the advantage of organic material and inorganic material, also can improve its mechanical strength and operational stability simultaneously.The preparation condition gentleness has been avoided the use of acid base catalysator, organic solvent, and granular size is controlled, the scope of application is wider.This method prepares hybrid microspheres size homogeneous, good stability, favorable repeatability.The present invention is suitable to have the immobilization of bioactive substances such as enzyme, antibody.
Description of drawings
Fig. 1 is the organic/inorganic hybridized microcapsule photo of embodiment 1-3 preparation.
Fig. 2 is profile scanning Electronic Speculum (SEM) photo of organic/inorganic hybridized microcapsule.
Fig. 3 is organic microcapsule photo of Comparative Examples 1 preparation.
The specific embodiment
Be described in further detail technical scheme of the present invention below in conjunction with example.
The ion concentration of solution in table 1 human plasma and the different simulated body fluids (mM/liter)
Figure G2009100708086D0000031
Embodiment 1
Preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 30.0mmol/LCa 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-Preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 50.0mmol/LHPO 4 2-, 0.5mmol/L SO 4 2-
Sodium alginate is dissolved in the simulated body fluid (II), is made into that to contain the sodium alginate mass fraction be 1.0% solution.Chitosan is dissolved in contains in the simulated body fluid (I), be made into the chitosan-containing mass fraction and be 0.5% solution.At room temperature, be that the 5ml syringe of 0.5mm drips the sodium alginate soln for preparing with the needle tubing diameter in chitosan solution, droplet chitosan be dissolved in preserve 20 minutes in simulated body fluid (I) after taking-up, be placed on rinsing in the distilled water then.All steps all are to carry out under room temperature and pH are 7 condition.
Embodiment 2
Preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 60.0mmol/LCa 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-Preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 100.0mmol/L HPO 4 2-, 0.5mmol/L SO 4 2-
Sodium alginate is dissolved in the simulated body fluid (II), is made into that to contain the sodium alginate mass fraction be 2.0% solution.Chitosan is dissolved in the simulated body fluid (I), is made into the chitosan-containing mass fraction and is 0.8% solution.At room temperature, be that the 5ml syringe of 0.9mm drips the sodium alginate soln for preparing with the needle tubing diameter in chitosan solution, prepare polysaccharide microcapsule with the hydroxyapatite biomimetic mineralization.Droplet is taken out after preserving 30 minutes being dissolved at chitosan in the simulated body fluid (I), is placed on rinsing in the distilled water then.All steps all are to carry out under room temperature and pH are 7 condition.
Embodiment 3
Preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 120.0mmol/LCa 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-Preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 200.0mmol/L HPO 4 2-, 0.5mmol/L SO 4 2-
Sodium alginate is dissolved in the simulated body fluid (II), is made into that to contain the sodium alginate mass fraction be 3.0% solution.Chitosan is dissolved in the simulated body fluid (I), is made into the chitosan-containing mass fraction and is 1.2% solution.At room temperature, be that the 5ml syringe of 1.5mm drips the sodium alginate soln for preparing with the needle tubing diameter in chitosan solution, prepare polysaccharide microcapsule with the hydroxyapatite biomimetic mineralization.Droplet is dissolved in the simulated body fluid (I) at chitosan to be taken out after preserving 50 minutes, is placed on rinsing in the distilled water then.All steps all are to carry out under room temperature and pH are 7 condition.
Comparative Examples 1
Preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 120.0mmol/LCa 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-Preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 0.5mmol/LSO 4 2-
Sodium alginate is dissolved in to contain in the simulated body fluid (II) (removes HPO 4 2-Other composition is constant in addition), be made into that to contain the sodium alginate mass fraction be 2.0% solution.Chitosan is dissolved in contains in the simulated body fluid (I), be made into the chitosan-containing mass fraction and be 0.8% solution.At room temperature, be that the 5ml syringe of 0.9mm adds that to drip the mass fraction for preparing be 2.0% sodium alginate soln in the chitosan solution with the needle tubing diameter, prepare polysaccharide microcapsule with the hydroxyapatite biomimetic mineralization.Droplet is dissolved at chitosan to be taken out after simulated body fluid (I) is preserved 30 minutes, is placed on rinsing in the distilled water then.All steps all are to carry out under room temperature and pH are 7 condition.

Claims (2)

1. a biomimetic way by simulated body fluid method prepares organic/inorganic hybridized microcapsule, it is characterized in that it is in simulated body fluid, with sodium alginate and chitosan is the feedstock production hybridized microcapsule, the mass fraction of sodium alginate soln is 1.0%-3.0%, the mass fraction 0.5%-1.2% of chitosan solution, concrete technology: the simulated body fluid solution of sodium alginate and the simulated body fluid of chitosan contain Ca 2+Ion solution reaction generates the polysaccharide microcapsule of hydroxyapatite biomimetic mineralization, is dissolved in simulated body fluid (I) after the placement at chitosan, uses water rinse.
2. a biomimetic way by simulated body fluid method prepares the preparation method of organic/inorganic hybridized microcapsule, it is characterized in that may further comprise the steps:
1) preparation contains simulated body fluid (I), and concrete composition is: 134.0mmol/L Na +, 5.0mmol/L K +, 30~120.0mmol/L Ca 2+, 3.0mmol/L Mg 2+, 258.0mmol/L Cl -, 0.5mmol/L SO 4 2-
2) preparation simulated body fluid (II), concrete composition is 350.0mmol/L Na +, 5.0mmol/L K +, 8.4mmol/L HCO 3 -, 148.0mmol/L Cl -, 50~200.0mmol/L HPO 4 2-, 0.5mmol/L SO 4 2-
3) sodium alginate is dissolved in the simulated body fluid (II), being made into mass fraction is the 1.0%-3.0% sodium alginate soln.
4) chitosan is dissolved in the simulated body fluid (I), is made into mass fraction 0.5%-1.2% and contains Ca 2+Ionic chitosan solution;
5) be under 7 the condition at room temperature, sodium alginate soln is added in the chitosan solution, stir, obtain the polysaccharide microcapsule droplet of hydroxyapatite biomimetic mineralization with pH;
6) the microcapsule droplet is preserved in chitosan solution after 20-50 minute and is taken out, and is placed on rinsing in the water then.
CN200910070808A 2009-10-15 2009-10-15 Organic/inorganic hybridized microcapsule prepared in biomimetic way by simulated body fluid method and preparation method thereof Pending CN101693021A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102658068A (en) * 2012-05-03 2012-09-12 天津大学 Polyacrylamide-titanium oxide hybrid porous microcapsules and preparation method
CN117159489A (en) * 2023-10-31 2023-12-05 潍坊医学院 Enteric hollow capsule and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102658068A (en) * 2012-05-03 2012-09-12 天津大学 Polyacrylamide-titanium oxide hybrid porous microcapsules and preparation method
CN117159489A (en) * 2023-10-31 2023-12-05 潍坊医学院 Enteric hollow capsule and preparation method thereof
CN117159489B (en) * 2023-10-31 2024-02-23 潍坊医学院 Enteric hollow capsule and preparation method thereof

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