Double-crosslinked chitosan hydrogel as well as preparation method and application thereof
A double-crosslinking and chitosan technology, applied in the field of biomaterials, can solve the problems of high toxicity of the crosslinking agent epichlorohydrin, long chemical crosslinking reaction time, and inability to realize rapid prototyping, etc., and achieve fast curing speed and preparation Fast response, improved mechanical strength and elasticity
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[0024] The present invention provides a kind of preparation method of double-crosslinked chitosan hydrogel on the one hand, and preparation method provided by the present invention mainly comprises:
[0025] The hydrogel obtained by the reaction of α-β unsaturated acylated chitosan and mercaptolated chitosan is soaked in ethanol solution to obtain double cross-linked chitosan hydrogel.
[0026] In the above preparation method, the double cross-linked chitosan hydrogel is prepared by chemical cross-linking and physical cross-linking methods. Different from the preparation method using epichlorohydrin as a crosslinking agent used in the prior art, the first step of crosslinking in the present invention is carried out by clicking addition of mercapto groups. Before the addition reaction, maleic anhydride and mercapto groups are used to Succinic acid is used to chemically modify chitosan, and the modified chitosan is used to derive itself as a cross-linking agent, and an addition ...
Embodiment approach
[0040] In some preferred embodiments of the present invention, the α-β unsaturated acylated chitosan as the hydrogel preparation raw material includes the following formula (i) compound:
[0041]
[0042] Among them, in formula (i), R 1 Removal of amino residues for chitosan;
[0043] R 2 , R 3 , R 4 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
[0044] As preferred, R 2 , R 3 , R 4Each independently is hydrogen, a substituted or unsubstituted alkyl group with 1-20 carbon atoms (preferably a substituted or unsubstituted alkyl group with 1-12 carbon atoms, more preferably a substituted or unsubstituted alkyl group with 1-6 carbon atoms Or unsubstituted alkyl, such as, but not limited to: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, etc.) of substituted or unsubstituted alkyl, carbon A substituted or ...
Embodiment 1
[0103] 1) Add 1.5g chitosan (molecular weight is about 50,000, deacylation degree is about 80%) into 0.01% (m / m) acetic acid solution, stir well and then sonicate for 30min;
[0104] Add 1.8g of maleic anhydride into 10ml of acetone and stir to dissolve, then add the resulting solution into the chitosan solution, stir and mix evenly, and react at 40°C for 2h;
[0105] After the reaction, the reaction solution was dialyzed for 3 days, during which the dialysate was replaced every 5 hours, and the resulting product was freeze-dried to obtain the product α-β unsaturated acylated chitosan (abbreviated as MCS).
[0106] Step 1) The reaction formula can be referred to as follows:
[0107]
[0108] 2) Add 1.5g of mercaptosuccinic acid into double distilled water and stir to dissolve, then add 1.2g of EDC and 300mg of NHS, after mixing thoroughly, adjust the pH of the solution to 6.5 with 1M NaOH, and continue stirring and mixing;
[0109] Add 1.5 g of chitosan to 0.01% (m / m) acet...
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Abstract
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