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马来酰化琼脂糖/PNIPAAm 接枝共聚物的制备与表征及其与壳聚糖形成聚电解质复合物。

Preparation and characterization of maleoylagarose/PNIPAAm graft copolymers and formation of polyelectrolyte complexes with chitosan.

机构信息

Departamento de Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile, Av. L. B. O'Higgins 3363, Santiago, Chile.

Departamento de Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile, Av. L. B. O'Higgins 3363, Santiago, Chile.

出版信息

Carbohydr Polym. 2018 Feb 15;182:81-91. doi: 10.1016/j.carbpol.2017.11.012. Epub 2017 Nov 8.

Abstract

A water soluble derivative in 98% yield with 23.1% incorporation of maleoyl groups was obtained by esterification of agarose with maleic anhydride. Graft copolymers were synthesized through vinyl groups of maleoylagarose with N-isopropylacrylamide using ceric ammonium nitrate or ammonium persulfate as initiator, by conventional method or microwave irradiation. High nitrogen content (4.6%) was obtained in the grafting process using ceric ammonium nitrate as initiator without microwave irradiation. Copolymers were characterized by FT-IR and NMR spectroscopies, TGA, DSC and morphological analysis by AFM and SEM microscopy, confirming the grafting of PNIPAAm onto polysaccharide backbone. Hydrogel films were obtained by ionic complexation between opposite charged groups of maleoylagarose-g-poly(N-isopropylacrylamide) and chitosan. The swelling of 1:1w/v maleoylagarose-g-PNIPAAm:chitosan film was higher than 2:1w/v film at 25 and 37°C. 53% release in vitro of diclofenac sodium from 1:1w/v maleoylagarose-g-PNIPAAm:chitosan was obtained at 37°C and pH 6.0 with <0.5 diffusional constant values.

摘要

通过马来酸酐与琼脂糖的酯化反应,得到了一种产率为 98%、马来酰基团含量为 23.1%的水溶性衍生物。通过硝酸铈铵或过硫酸铵作为引发剂,采用常规方法或微波辐射,使马来酰化琼脂糖的乙烯基与 N-异丙基丙烯酰胺发生接枝共聚反应。使用硝酸铈铵作为引发剂,在没有微波辐射的情况下,接枝过程中可以得到高氮含量(4.6%)。通过傅里叶变换红外光谱和核磁共振光谱、热重分析、差示扫描量热法和原子力显微镜及扫描电子显微镜的形态分析对共聚物进行了表征,证实了 PNIPAAm 接枝到多糖主链上。通过马来酰化琼脂糖-g-聚(N-异丙基丙烯酰胺)和壳聚糖的相反电荷基团之间的离子络合作用,得到了水凝胶薄膜。在 25 和 37°C 下,1:1w/v 马来酰化琼脂糖-g-PNIPAAm:壳聚糖薄膜的溶胀率高于 2:1w/v 薄膜。在 37°C 和 pH 6.0 下,1:1w/v 马来酰化琼脂糖-g-PNIPAAm:壳聚糖可得到 53%的双氯芬酸钠体外释放,扩散常数值小于 0.5。

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