Direct sulfation of bacterial cellulose with a ClSO3H/DMF complex and structure characterization of the sulfates
Direct sulfation of bacterial cellulose with a ClSO3H/DMF complex and structure characterization of the sulfates
复制标题
用 ClSO3H/DMF 复合物直接硫酸化细菌纤维素以及硫酸盐的结构表征
DOI：
10.1002/pat.3218
复制
发表时间：
2014-02-01
影响因子：
3.4
通讯作者：
Qin, Ziyu
中科院分区：
文献类型：
--
作者：
Zhu, Li;Qin, Jinmin;Qin, Ziyu
细菌纤维素（BC）是微生物合成的纤维素形式，具有独特的结构特性，不同于植物纤维素。迄今为止，BC的化学改性尚未得到广泛研究。本文旨在以ClSO3H/DMF复合物为硫酸化剂，在N,N-二甲基甲酰胺（DMF）中制备细菌纤维素硫酸钠（SBS）。合成了不同硫酸化程度（DS，0.04-0.86）的SBS。在硫酸化过程中，体系可以从非均相变为均相。就 DS 而言，最佳 ClSO3H 用量和反应时间分别为 6 mol/mol 脱水葡萄糖单位和 4 h。升高温度，DS略有增加，但产率明显下降。 DS≥0.24的SBS可溶于去离子水。碳核磁共振谱显示硫酸化反应的顺序为C-6 > C-2 > C-3。 X射线衍射图表明BC的晶体结构在硫酸化过程中被破坏。 BC在硫酸化和解聚过程中都比微晶纤维素具有更好的反应活性。 SBS是一种潜在的生物材料。然而，BC在目前的硫酸盐化过程中明显解聚，限制了SBS在材料中的应用。应尽可能完全除去反应混合物的水分，以保证有效的硫酸化并减少解聚。版权所有 © 2013 约翰·威利父子有限公司
Bacterial cellulose (BC) is a form of cellulose synthesized by microorganisms, which has unique structure properties and differs from plant cellulose. Up to now, chemical modification of BC has not been studied widely. This paper aims to prepare sodium bacterial cellulose sulfate (SBS) in N,N-dimethylformamide (DMF) with a ClSO3H/DMF complex as the sulfating agent. SBSs with diverse degree of sulfation (DS, 0.04–0.86) were synthesized. The system could change from heterogeneous to homogeneous during the sulfation. Regarding to the DS, the optimal ClSO3H amount and reaction time were 6 mol/mol anhydroglucose unit and 4 h, respectively. DS increased a little when increasing the temperature, while the yield decreased significantly. SBSs with DS > 0.24 were soluble in deionized water. Carbon nuclear magnetic resonance spectroscopy revealed that the sulfation prefers to take place in the order of C-6 > C-2 > C-3. The X-ray diffraction profiles indicated that the crystalline structure of BC was destroyed during sulfation. BC has better reactivity than microcrystalline cellulose in both sulfation and depolymerization processes. SBS is a potential biomaterial. However, BC depolymerized obviously in present sulfation, which forbids application of SBS in material. Moisture of the reaction mixture should be removed as completely as possible to guarantee efficient sulfation and decrease depolymerization. Copyright © 2013 John Wiley & Sons, Ltd.