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甲氧基聚乙二醇-壳聚糖的性质与物理化学性质。

Characterization and physical-chemistry of methoxypoly(ethylene glycol)-g-chitosan.

机构信息

Sao Carlos Institute of Chemistry, University of Sao Paulo, Avenida Trabalhador sao-carlense, 400, CEP 13566-590 Sao Carlos, SP, Brazil.

Sao Carlos Institute of Chemistry, University of Sao Paulo, Avenida Trabalhador sao-carlense, 400, CEP 13566-590 Sao Carlos, SP, Brazil.

出版信息

Int J Biol Macromol. 2019 Mar 1;124:828-837. doi: 10.1016/j.ijbiomac.2018.11.246. Epub 2018 Nov 28.

Abstract

Methoxypoly(ethyleneglycol)-graft-chitosan (PEG-g-Ch) was prepared by grafting polyethyleneglycol into chitosans (Ch) exhibiting different average degree of deacetylation (60% < DD¯ < 95%). H NMR showed that PEG-g-Ch derivatives presented high average degree of N-substitution (DS¯ ≈ 40%) and such derivatives exhibited full water solubility at 1.0 < pH < 11.0. The mPEG-g-Ch derivatives displayed much lower intrinsic viscosity (20 mL g < [η] < 110 mL g) as compared to the parent chitosans (440 mL g < [η] < 1650 mL g) due to extensive exposition of PEG chains to the aqueous medium and compact coiling of the chitosan backbone. The presence of numerous PEG chains grafted into chitosan also determined the crystalline arrangement and the thermal stability of PEG-g-Ch derivatives. The rheological study showed that the concentrated aqueous solutions of PEG-g-Ch derivatives displayed pseudoplastic behavior regardless of the parent chitosans´ characteristics and no dependence of dynamic viscosity on the temperature. However, PChD2 (DD¯ ≈ 76%; [η] ≈ 1201 mL g) showed a distinct rheological behavior as it formed a physically cross-linked hydrogel that exhibited a thermo-induced sol-gel transition at ≈38 °C.

摘要

甲氧基聚(乙二醇)-接枝壳聚糖(PEG-g-Ch)通过将聚乙二醇接枝到壳聚糖(Ch)上制备,壳聚糖的平均脱乙酰度(60%<DD¯<95%)不同。1H NMR 表明,PEG-g-Ch 衍生物具有较高的平均 N-取代度(DS¯≈40%),在 1.0<pH<11.0 时,这些衍生物完全溶于水。与母体壳聚糖(440mLg<[η]<1650mLg)相比,mPEG-g-Ch 衍生物的特性粘数(20mLg<[η]<110mLg)要低得多,这是由于 PEG 链广泛暴露于水介质中和壳聚糖主链的紧密卷曲。许多 PEG 链接枝到壳聚糖上也决定了 PEG-g-Ch 衍生物的结晶排列和热稳定性。流变学研究表明,PEG-g-Ch 衍生物的浓水溶液表现出假塑性行为,而与母体壳聚糖的特性无关,且动态粘度不受温度的影响。然而,PChD2(DD¯≈76%;[η]≈1201mLg)表现出明显的流变行为,因为它形成了一种物理交联的水凝胶,在约 38°C 时表现出热诱导的溶胶-凝胶转变。

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