CN102219938A - Preparation method of hydrophobically modified sodium alginate - Google Patents
Preparation method of hydrophobically modified sodium alginate Download PDFInfo
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- CN102219938A CN102219938A CN2010101470383A CN201010147038A CN102219938A CN 102219938 A CN102219938 A CN 102219938A CN 2010101470383 A CN2010101470383 A CN 2010101470383A CN 201010147038 A CN201010147038 A CN 201010147038A CN 102219938 A CN102219938 A CN 102219938A
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Abstract
A preparation method of hydrophobically modified sodium alginate gel belongs to the technical field of biomedical materials. The invention prepares a star polymer which contains inorganic matter and hydrophobic polymers; the prepared polymer is ultrasonically dispersed into a sodium alginate solution by ultrasonic dispersion technology; and a calcium alginate hybrid gel with both hydrophobicity and hydrophilicity is prepared by a dropping liquid method. A hydrophobic drug of ibuprofen has a high embedding rate of up to above 90% in the gel, and has a good sustained release effect with a drug release amount of the first 2 hours being reduced by nearly 45%; the problem is overcome that since sodium alginate has strong hydrophilicity and the loading amount for hydrophobic drugs is less, burst release is easy to occur in an early stage of drug release. The drug-loaded microsphere of the invention is convenient for preparation, controllable in particle size (about 1 mm), good in biocompatibility, has no toxicity to human body, and has potential application value for being used as a drug carrier.
Description
Technical field
A kind of preparation method about the hydrophobically modified sodium alginate gel belongs to the bio-medical material technical field.
Background technology
Sodium alginate is the macromolecular compound that extracts from brown alga, and raw material sources are abundant, have excellent biological compatibility, and are biodegradable to biological tissue's non-immunogenicity, and degraded product is nontoxic; With other polymer phase ratios, price is low, better wetting ability is enriched, had in the source, is easy to cell absorption, and nutritive substance is easy to characteristics such as infiltration; Compare with other natural polymer, under mild conditions, can form the gel that meets multiple performance requriements, therefore in grocery trade, cosmetic industry and pharmaceutical sector, have widely and use with the divalent calcium positively charged ion.Wherein, in pharmaceutical industries, sodium alginate is widely used as multiple delivery systems such as preparation pill, pulvis, tablet for many years as pharmaceutical carrier.But aspect the embedding hydrophobic drug, no matter above-mentioned formulation still medicine stability increase aspect is all existing very big defective from slow release effect, embedding rate, makes that total bioavailability is less.
Yet many good hydrophobic drugs such as Ibuprofen BP/EP, Zorubicin, itraconazole etc. all are being quite good medicines aspect the treatment disease, but their solvabilities in sodium alginate gel are little, and availability is lower, and application is restricted.Taked multiple research method in order to improve the availability people, as: thus total specific surface area increase solubleness, particle crystallization, spray-drying process or the like increased by grinding, but these methods all have shortcoming separately, and are wide etc. as bad dispersibility, poor stability, size-grade distribution.
Summary of the invention
The object of the present invention is to provide a kind of preparation method about the hydrophobically modified sodium alginate gel, material involved in the present invention is (to be called for short POSS-(OH) with poly-hydroxy cage modle eight polysilsesquioxanes
32) for nuclear, poly(lactic acid) are the star-type polymer of chain, in sodium alginate, adopt sessile drop method to make calcium alginate gel its ultra-sonic dispersion, improve the drug loading amount effectively, make it have slow release effect preferably.
Advantages such as the present invention makes full use of that the natural biological polysaccharide-the sodium alginate inherent is nontoxic, good water solubility, biocompatibility are better are carried out it hydrophobically modified and are made microballoon, and promptly synthetic a kind of novel biological degradable material is as pharmaceutical carrier.
Laboratory homemade star-type polymer (Fig. 1) is the inorganic-organic hybrid material, it is a nuclear with Si-O-Si cage modle hexahedron structure, and poly(lactic acid) is a side chain, can be used as the hydrophobic drug warehousing storage, biocompatibility is fine, and the metabolic in vivo final product of poly(lactic acid) is CO
2And H
2O, intermediate product lactic acid also are eubolism products in the body, so do not gather at vitals.In addition, interact by force, can greatly improve the charge capacity of hydrophobic drug, can slow down the release rate of medicine simultaneously with hydrophobic drug.
The preparation method of hydrophobically modified sodium alginate micro ball: make the laboratory by oneself star-type polymer and be dissolved in the dimethyl sulfoxide solution, under high-speed stirring, join in the sodium alginate soln, after 20 minutes, disperseed 2 minutes with ultrasonoscope; Draw this solution with syringe, solution is splashed into the CaCl of concentration 3% by sessile drop method
2In the solution, slaking, washing, drying obtain the microballoon that makes at last.
Advantage of the present invention:
1. raw material of the present invention is a natural seaweed acid sodium, and biocompatibility, degradation property are good and cheap.The synthetic star-type polymer is nuclear with POSS, and poly(lactic acid) is a chain, and nontoxic, nonirritant also has excellent biological compatibility, and degradability is good.
2. adopt the hydrogel of drop legal system, method is simple to operation, and it is more regular that form is circle, and size is consistent.
3. can increase the embedding rate of hydrophobic drug in sodium alginate, delay release rate, therefore can be used as pharmaceutical carrier, be used for multiple the medicine especially embedding and the release of hydrophobic drug.
Description of drawings
Fig. 1 a POSS-PLA, POSS is nuclear for the nuclear poly(lactic acid) is the star polymer of chain with the cage modle siloxanes, poly(lactic acid) is the star-type polymer of chain; B hydrophobically modified sodium alginate gel micropill structural representation, the red POSS-PLA that represents.
The hydrophobically modified microsphere drug release profiles that Fig. 2 makes for embodiment 1,2,3.
The hydrophobically modified microsphere drug release profiles that Fig. 3 makes for embodiment 1,4,5.
Embodiment
Embodiment 1
Get a certain amount of Ibuprofen BP/EP and 100mg POSS-PLA (Mn=6.22 * 10
4) be dissolved in methyl-sulphoxide, under high-speed stirring, splash into the 50mL massfraction and be in 2% the sodium alginate aqueous solution, and continue to stir 20 minutes, with ultrasonic 2 minutes of self-control Vltrasonic device, get its mixing solutions then, splashing into concentration with the 6# medical needle is 3% CaCl
2In the solution, slaking 2 hours, gel distilled water flushing 3 times, filtering separation, cryodrying promptly makes the hydrophobically modified sodium alginate micro ball.
The relative molecular mass that adds star-type polymer POSS-PLA is 2.51 * 10
4, other steps are identical with embodiment 1.
Embodiment 3
The relative molecular mass that adds star-type polymer POSS-PLA is 14.85 * 10
4, other steps are identical with embodiment 1.
The mass ratio of sodium alginate and POSS-PLA is 100: 5, and other steps are identical with embodiment 1.
Embodiment 5
The mass ratio of sodium alginate and POSS-PLA is 100: 15, and other steps are identical with embodiment 1.
The sodium alginate micro ball release profiles that star-like poly(lactic acid) content is different: take by weighing the microballoon sample of certain mass example 1, example 2, example 3 preparations,, under the 200mL pH 7.2 phosphate buffered saline buffer conditions, measure drug releasing rate, draw release profiles at 37 ℃.
Method for preparing medicine carrying microballoons embedding rate reaches more than 90%, and increase along with the increase of star-like poly(lactic acid), and drug releasing rate is along with the increase of star-like poly(lactic acid) content descend (Fig. 2), because star-type polymer is a nuclear with the cage modle siloxanes, the hydrophobicity poly(lactic acid) is a chain, can be used as the medicament storage warehouse, strengthen, make medicine dissolution rate from sodium alginate micro ball reduce with the interaction of hydrophobic drug.This medicine carrying microballoons has slow release effect preferably as seen from the figure, and its sustained release rate can recently be controlled by the quality of regulating star-type polymer and sodium alginate.
Embodiment 7
The release profiles that contains the sodium alginate micro ball of different molecular weight star-type polymer: the microballoon sample that takes by weighing certain mass example 1, example 4, example 5 preparations, at 37 ℃, under the 200mL pH 7.2 phosphate buffered saline buffer conditions, measure drug releasing rate, draw release profiles.
As seen from Figure 3, under the situation that star-like poly(lactic acid) and sodium alginate mass ratio remain unchanged, increase along with the star-type polymer molecular weight, drug release rate reduces, the growth of poly(lactic acid) arm and the interaction of hydrophobic drug strengthen, thereby reduced the dissolution rate of medicine, therefore, the sustained release rate of medicine carrying microballoons can be regulated by the relative molecular mass of star-type polymer.
Claims (5)
1. hydrophobically modified sodium alginate hydrogel, it is the mixture of a kind of star-type polymer and sodium alginate, it is characterized in that with the laboratory make by oneself star-type polymer (Fig. 1 a) ultra-sonic dispersion in sodium alginate soln, adopt drip method to splash into and become gel glue in the calcium chloride water, promptly make hydrophobically modified sodium alginate gel (Fig. 1 b).
2. star-like poly(lactic acid) according to claim 1 is characterized in that with poly-hydroxy cage modle eight polysilsesquioxanes (POSS-(OH)
32) be nuclear, with D, the L-rac-Lactide carries out active ring-opening polymerization and obtains star-type polymer POSS-PLA.
3. the mass ratio of star-type polymer according to claim 1 and sodium alginate is 5: 100～15: 100.
4. the preparation method of hydrophobically modified sodium alginate hydrogel, get a certain amount of POSS-PLA and be dissolved in methyl-sulphoxide, under high-speed stirring, splash in the sodium alginate aqueous solution of massfraction 2%, and continue to stir 20 minutes, then with making Vltrasonic device by oneself ultrasonic 2 minutes, get its mixing solutions, splashing into concentration with the 6# medical needle is 3% CaCl
2In the solution, slaking 2 hours, gel distilled water flushing 3 times are filtered, and cryodrying promptly makes the hydrophobically modified sodium alginate micro ball.
5. according to claim 4, the volume ratio of solvent methyl-sulphoxide consumption and sodium alginate soln is 4%～6%.
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Cited By (10)
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| CN103130912A (en) * | 2011-12-02 | 2013-06-05 | 江南大学 | One-step method of preparing covalence crosslinked and hydrophobic modified sodium alga acid hydrogel |
| WO2015039277A1 (en) * | 2013-09-17 | 2015-03-26 | Colgate-Palmolive Company | Oral care composition |
| CN105601954A (en) * | 2016-01-28 | 2016-05-25 | 湖南工业大学 | Preparation method of biological friendly hydrogel with excellent rebound resilience |
| CN105963260A (en) * | 2016-06-27 | 2016-09-28 | 北京林业大学 | Preparation method of pH-sensitive type drug microspheres and pH-sensitive type drug microspheres prepared by preparation method |
| CN107964051A (en) * | 2017-07-31 | 2018-04-27 | 海南大学 | A kind of modified polymannuronate derivative, its load liquid medicine lotion and preparation method |
| CN108339526A (en) * | 2018-02-26 | 2018-07-31 | 西南科技大学 | Modified sodium alginate sorbing material and preparation method thereof for tetracycline antibiotics absorption |
| CN108774337A (en) * | 2018-06-22 | 2018-11-09 | 南京林业大学 | A kind of hydrophobically modified method of melamine sponge and products thereof and application |
| US10500147B2 (en) | 2014-01-24 | 2019-12-10 | Colgate-Palmolive Company | Toothpaste with alginate based rheology modifier |
| CN112358808A (en) * | 2020-10-27 | 2021-02-12 | 杭州华玮生物科技有限公司 | Pretreatment method for preventing cosmetic raw materials and freeze-dried powder from sticking to wall |
| CN113082215A (en) * | 2021-04-19 | 2021-07-09 | 苏州大学 | Bismuth selenide hydrogel, bismuth selenide hydrogel bacterial carrier, preparation method and application |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130912A (en) * | 2011-12-02 | 2013-06-05 | 江南大学 | One-step method of preparing covalence crosslinked and hydrophobic modified sodium alga acid hydrogel |
| WO2015039277A1 (en) * | 2013-09-17 | 2015-03-26 | Colgate-Palmolive Company | Oral care composition |
| US9713586B2 (en) | 2013-09-17 | 2017-07-25 | Colgate-Palmolive Company | Oral care composition |
| US10500147B2 (en) | 2014-01-24 | 2019-12-10 | Colgate-Palmolive Company | Toothpaste with alginate based rheology modifier |
| CN105601954A (en) * | 2016-01-28 | 2016-05-25 | 湖南工业大学 | Preparation method of biological friendly hydrogel with excellent rebound resilience |
| CN105963260A (en) * | 2016-06-27 | 2016-09-28 | 北京林业大学 | Preparation method of pH-sensitive type drug microspheres and pH-sensitive type drug microspheres prepared by preparation method |
| CN105963260B (en) * | 2016-06-27 | 2018-08-24 | 北京林业大学 | A kind of preparation method of pH responsive types medicine microspheres and the pH responsive type medicine microspheres prepared by this method |
| CN107964051B (en) * | 2017-07-31 | 2020-09-01 | 海南大学 | Drug-loaded aqueous emulsion containing modified polymannuronic acid derivative and preparation method thereof |
| CN107964051A (en) * | 2017-07-31 | 2018-04-27 | 海南大学 | A kind of modified polymannuronate derivative, its load liquid medicine lotion and preparation method |
| CN108339526A (en) * | 2018-02-26 | 2018-07-31 | 西南科技大学 | Modified sodium alginate sorbing material and preparation method thereof for tetracycline antibiotics absorption |
| CN108339526B (en) * | 2018-02-26 | 2020-07-31 | 西南科技大学 | Modified sodium alginate adsorption material for adsorbing tetracycline antibiotics and preparation method thereof |
| CN108774337A (en) * | 2018-06-22 | 2018-11-09 | 南京林业大学 | A kind of hydrophobically modified method of melamine sponge and products thereof and application |
| CN108774337B (en) * | 2018-06-22 | 2020-11-27 | 南京林业大学 | Hydrophobic modification method of melamine sponge, product and application thereof |
| CN112358808A (en) * | 2020-10-27 | 2021-02-12 | 杭州华玮生物科技有限公司 | Pretreatment method for preventing cosmetic raw materials and freeze-dried powder from sticking to wall |
| CN112358808B (en) * | 2020-10-27 | 2022-02-25 | 杭州华玮生物科技有限公司 | Pretreatment method for preventing cosmetic raw materials and freeze-dried powder from sticking to wall |
| CN113082215A (en) * | 2021-04-19 | 2021-07-09 | 苏州大学 | Bismuth selenide hydrogel, bismuth selenide hydrogel bacterial carrier, preparation method and application |
| CN113082215B (en) * | 2021-04-19 | 2022-01-18 | 苏州大学 | Bismuth selenide hydrogel, bismuth selenide hydrogel bacterial carrier, preparation method and application |
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Application publication date: 20111019 |