CN102093582A - Preparation method of radiation crosslinking hydrogel - Google Patents
Preparation method of radiation crosslinking hydrogel Download PDFInfo
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- CN102093582A CN102093582A CN 201110000326 CN201110000326A CN102093582A CN 102093582 A CN102093582 A CN 102093582A CN 201110000326 CN201110000326 CN 201110000326 CN 201110000326 A CN201110000326 A CN 201110000326A CN 102093582 A CN102093582 A CN 102093582A
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Abstract
The invention relates to a preparation method of radiation crosslinking hydrogel. The preparation method of the hydrogel comprises the following steps: preparing different mass concentrations of poly(L-glutamic acid) solutions, wherein the mass concentrations are 1-10wt%; strongly stirring for 1h, dropping a defined amount of NaOH, adjusting the pH value to 12, standing to defoam; irradiating the solution for 5-100min by electron beams with the dosage rate of 100Gy/s to ensure that polymer chains are crosslinked under the high energy radiation of electron beams, placing the prepared hydrogel in a dialysis bag, then soaking the bag in deionized water, changing water at regular intervals to remove residual small molecules and ions and obtain the poly(L-glutamic acid) radiation crosslinking hydrogel. The preparation method of radiation crosslinking hydrogel in the invention is simple; no crosslinking agent is added; and the obtained hydrogel is pure and has no impurity. By changing the concentration of the polymer solution and the radiation dosage of electron beams, the swelling degree of the prepared hydrogel can be regulated, thus hydrogel can be used in different application fields such as drug-carrying and drug-releasing system and tissue engineering.
Description
Technical field
The present invention relates to a kind of preparation method of biodegradable hydrogel, particularly a kind ofly be used for reaching crosslinked hydrogel preparation method by electron beam irradiation.
Background technology
High-molecular gel is meant a kind of macromolecular network of full of liquid, promptly by cancellated superpolymer and solvent composition.It is the three-dimensional network between liquid and solid, and the mobility of existing liquid-like and flowability have the form-stability of solid-like again.When the macromolecular skeleton possess hydrophilic property, its liquid that is full of can be the water or the aqueous solution, and this gel is called as hydrophilic gel, is called for short hydrogel.
According to hydrogel preparation method difference, can be divided into physical cross-linking hydrogel, chemically crosslinked aquagel and radiation crosslinking hydrogel.Physical cross-linking hydrogel is that the physical actions such as winding by hydrogen bond, electrostatic interaction, chain form, and can avoid using linking agent.This gel is volatile, can change solution into by the heating gel, so be also referred to as pseudo-gels or heat reversible gel.Since the physical crosslinking reactive force a little less than, destroyed when changing in ambient conditions (as pH value, ionic strength etc.) easily, mechanical property is relatively poor, so be subjected to certain restriction in practical application.Chemically crosslinked aquagel is by adding the hydrogel of suitable linking agent formation cross-linked network, performance is stable than physical gel, have higher cross-linking density and mechanical property preferably, and can control the aperture and the swelling capacity of gel by the consumption of regulating linking agent, be to study maximum hydrogels at present.Yet chemically crosslinked require polymer must have can with the functional group of linking agent reaction, for some special polymers that does not have reactive group, can not use this method.The radiation crosslinking hydrogel is to utilize high energy radiation such as gamma-rays or electron beam can make the generation of water-soluble polymer interchain crosslinked, forms macromolecule hydrogel.This method need not be added linking agent, and product is pure, simple to operate, thus more be applicable to the preparation of bio-medical material than chemical crosslink technique, and the swelling behavior of gel and mechanical property can be controlled by radiation dose.Chen Jie, Dan Ting etc. contain cyclodextrin structure copolymer aquagel (Chinese patent publication number CN101302275) with prepared by EB irradiation; Ruan Weiqing, Wang Xiaogong etc. are by the directly synthetic pH sensitive polymer hydrogel (Chinese patent publication number CN1974609) of electron beam irradiation polymerization; Ruan Weiqing, Liu Bin etc. directly synthesize pH sensitive aqueous gel (Chinese patent publication number CN1834111) with the ultraviolet radiation polymerization; But utilize the radiation crosslinking method to prepare one-component L-glutamic acid polypeptide macromolecule hydrogel at present and there is no report both at home and abroad, and test the result factually and show, can regulate the swelling capacity of the hydrogel that makes by the change of polymer solution concentration, doses of electron beam radiation, thereby realize that hydrogel is in different application Application for Field such as medicine carrying delivery system, organizational projects.
Summary of the invention
One of purpose of the present invention is, adopts the synthetic macromolecule with good biocompatibility and biodegradability, has the good hydrogel of intensity by the preparation of electron beam high-energy radiation.Working method is simple, need not add linking agent, pure, the inclusion-free of the hydrogel for preparing.
Two of purpose of the present invention is, by regulating doses of electron beam radiation and poly-L-glutamic acid acid solutions, regulates the swelling behavior degree that makes, thereby realizes that hydrogel is in the different application Application for Field.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of above-mentioned radiation crosslinking hydrogel is characterized in that the concrete steps of this method are:
(1) the preparation mass percentage concentration is the poly-L-glutamic acid aqueous acid of 1 ~ 10wt%, and wherein the L-glutamic acid molecular weight is 20000 ~ 100000, and the powerful then 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation;
(2) the poly-L-glutamic acid aqueous acid being placed radiation dose rate is irradiation 5 ~ 100min under 50 ~ 500Gy/s electron beam, obtains the L-glutamic acid hydrogel;
(3) hydrogel that makes is packed into dialysis tubing is put into deionized water then and is soaked, and changes deionized water one time every 4h, changes altogether 8 times, to remove residual small molecules and ion.
The present invention is a raw material with the L-glutamic acid, utilize the electron beam high-energy radiation to make between macromolecular chain to take place crosslinked, good thereby preparation has intensity, biodegradable hydrogel.Be characterized in the poly-L-glutamic acid aqueous acid is made hydrogel by the electron beam high-energy radiation, do not need to add other component, can not introduce impurity.This invention is simple to operate, and the pure inclusion-free of system has good swelling behavior, and a kind of new bio-medical material with good biocompatibility can be provided, and can be applicable to bio-medical material.
Embodiment:
Describe the present invention below in conjunction with embodiment.
Embodiment one:
L-glutamic acid (molecular weight 5w) aqueous solution of preparation massfraction 5%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 10 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 305%.
Embodiment two:
L-glutamic acid (molecular weight 5w) aqueous solution of preparation massfraction 10%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 10 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 674%.
Embodiment three:
L-glutamic acid (molecular weight 10w) aqueous solution of preparation massfraction 5%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 20 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 1822%.
Embodiment four:
L-glutamic acid (molecular weight 10w) aqueous solution of preparation massfraction 5%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 40 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 1100%.
Embodiment five:
L-glutamic acid (molecular weight 10w) aqueous solution of preparation massfraction 10%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 20 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 1544%.
Embodiment six:
L-glutamic acid (molecular weight 10w) aqueous solution of preparation massfraction 10%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 30 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 962%.
Embodiment seven:
L-glutamic acid (molecular weight 2w) aqueous solution of preparation massfraction 10%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 20 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 738%.
Embodiment eight:
L-glutamic acid (molecular weight 5w) aqueous solution of preparation massfraction 10%wt, the powerful 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, and it is dissolved fully, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation.This solution was placed under the dose rate 100Gy/s electron beam irradiation 20 minutes,, put into deionized water then and soak the hydrogel that the makes dialysis tubing of packing into, change deionized water one time every 4h, change altogether 8 times, to remove residual small molecules and ion, the swelling behavior degree of gained is 1376%.
Claims (1)
1. the preparation method of a radiation crosslinking hydrogel is characterized in that the concrete steps of this method are as follows:
(1) the preparation mass percentage concentration is the poly-L-glutamic acid aqueous acid of 1 ~ 10wt%, and wherein the L-glutamic acid molecular weight is 20000 ~ 100000, and the powerful then 1h that stirs regulates poly-L-glutamic acid aqueous acid pH=12 with NaOH, leaves standstill de-bubble; This solution is enclosed small size valve bag, feed the nitrogen deoxygenation;
(2) the poly-L-glutamic acid aqueous acid being placed radiation dose rate is irradiation 5 ~ 100min under 50 ~ 500Gy/s electron beam, obtains the L-glutamic acid hydrogel;
(3) hydrogel that makes is packed into dialysis tubing is put into deionized water then and is soaked, and changes deionized water one time every 4h, changes altogether 8 times, to remove residual small molecules and ion.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044588A (en) * | 2012-12-26 | 2013-04-17 | 杭州飞捷科技有限公司 | Solid hydrogel and preparation method thereof |
| CN103071181A (en) * | 2013-02-01 | 2013-05-01 | 刘昌桂 | Hydrogel as well as preparation method and purpose of hydrogel |
| WO2016082725A1 (en) * | 2014-11-27 | 2016-06-02 | 华东理工大学 | Method for preparing non-free radical photochemical crosslinking hydrogel material, and product and application thereof |
| CN105686971A (en) * | 2016-01-20 | 2016-06-22 | 南京轩凯生物科技有限公司 | Polyamino acid gel and preparation method and application thereof |
| CN107802894A (en) * | 2017-10-11 | 2018-03-16 | 广州新诚生物科技有限公司 | A kind of bio-medical gel and preparation method thereof |
| CN115058036A (en) * | 2022-06-17 | 2022-09-16 | 康健仿生(清远)科技有限公司 | Cross-linked polyglutamic acid composite gel membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007593A1 (en) * | 2002-07-10 | 2004-01-22 | Bioleaders Corp | Poly-gamma-glutamate having ultra high molecular weight and method for using the same |
| CN1730105A (en) * | 2005-08-11 | 2006-02-08 | 南开大学 | Process for preparing super strength water absorbent from polyglutamic acid prepared by microbe fermentation and synthesis |
| CN1974432A (en) * | 2005-12-02 | 2007-06-06 | 东海生物科技股份有限公司 | Use of gamma- polyglutamic acid, gamma- polyglutamate and/ or its aqueous gel for removing heavy metal and dissolving calcium and/ or magnesium scale |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007593A1 (en) * | 2002-07-10 | 2004-01-22 | Bioleaders Corp | Poly-gamma-glutamate having ultra high molecular weight and method for using the same |
| CN1730105A (en) * | 2005-08-11 | 2006-02-08 | 南开大学 | Process for preparing super strength water absorbent from polyglutamic acid prepared by microbe fermentation and synthesis |
| CN1974432A (en) * | 2005-12-02 | 2007-06-06 | 东海生物科技股份有限公司 | Use of gamma- polyglutamic acid, gamma- polyglutamate and/ or its aqueous gel for removing heavy metal and dissolving calcium and/ or magnesium scale |
Non-Patent Citations (1)
| Title |
|---|
| 《离子交换与吸附》 20070430 刘静等 利用 60Cogamma-射线制备微生物聚谷氨酸类吸水剂及其吸水性能研究 第129-136页，第2.1、2.2、2.4节 1 第23卷, 第2期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044588A (en) * | 2012-12-26 | 2013-04-17 | 杭州飞捷科技有限公司 | Solid hydrogel and preparation method thereof |
| CN103044588B (en) * | 2012-12-26 | 2016-07-06 | 杭州飞捷科技有限公司 | A kind of solid hydrogel and preparation method thereof |
| CN103071181A (en) * | 2013-02-01 | 2013-05-01 | 刘昌桂 | Hydrogel as well as preparation method and purpose of hydrogel |
| CN103071181B (en) * | 2013-02-01 | 2015-04-29 | 刘昌桂 | Hydrogel as well as preparation method and purpose of hydrogel |
| WO2016082725A1 (en) * | 2014-11-27 | 2016-06-02 | 华东理工大学 | Method for preparing non-free radical photochemical crosslinking hydrogel material, and product and application thereof |
| US10294335B2 (en) | 2014-11-27 | 2019-05-21 | Zhongshan Guanghe Medical Technology Co., Ltd | Preparation method, product and application of non-free radical photo-crosslinked hydrogel material |
| CN105686971A (en) * | 2016-01-20 | 2016-06-22 | 南京轩凯生物科技有限公司 | Polyamino acid gel and preparation method and application thereof |
| CN107802894A (en) * | 2017-10-11 | 2018-03-16 | 广州新诚生物科技有限公司 | A kind of bio-medical gel and preparation method thereof |
| CN115058036A (en) * | 2022-06-17 | 2022-09-16 | 康健仿生(清远)科技有限公司 | Cross-linked polyglutamic acid composite gel membrane and preparation method and application thereof |
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Application publication date: 20110615 |