Intermolecular Interactions and 3D Structure in Cellulose-NaOH-Urea Aqueous System

被引:98
作者
Jiang, Zhiwei [1 ,2 ]
Fang, Yan [2 ]
Xiang, Junfeng [1 ]
Ma, Yanping [1 ]
Lu, Ang [2 ]
Kang, Hongliang [1 ]
Huang, Yong [1 ]
Guo, Hongxia [1 ]
Liu, Ruigang [1 ]
Zhang, Lina [2 ]
机构
[1] Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, State Key Lab Polymer Phys & Chem, Beijing 100190, Peoples R China
[2] Wuhan Univ, Dept Chem, Wuhan 430072, Peoples R China
基金
国家自然科学基金重大项目; 中国国家自然科学基金;
关键词
HYDROGEN-BONDING SYSTEM; SYNCHROTRON X-RAY; IONIC LIQUID; DENSITY FUNCTIONALS; MAGNETIC-RESONANCE; CRYSTAL-STRUCTURE; NMR ANALYSIS; DISSOLUTION; CHLORIDE; MECHANISM;
D O I
10.1021/jp501408e
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The dissolution of cellulose in NaOH/urea aqueous solution at low temperature is a key finding in cellulose science and technology. In this paper, N-15 and Na-23 NMR experiments were carried out to clarify the intermolecular interactions in cellulose/NaOH/urea aqueous solution. It was found that there are direct interactions between OH- anions and amino groups of urea through hydrogen bonds and no direct interaction between urea and cellulose. Moreover, Na+ ions can interact with both cellulose and urea in an aqueous system. These interactions lead to the formation of cellulose-NaOH-urea-H2O inclusion complexes (ICs). Na-23 relaxation results confirmed that the formation of urea-OH- clusters can effectively enhance the stability of Na+ ions that attracted to cellulose chains. Low temperature can enhance the hydrogen bonding interaction between OH- ions and urea and improve the binding ability of the NaOH/urea/H2O clusters that attached to cellulose chains. Cryo-TEM observation confirmed the formation of cellulose-NaOH-urea-H2O ICs, which is in extended conformation with mean diameter of about 3.6 nm and mean length of about 300 nm. Possible 3D structure of the ICs was proposed by the M06-2X/6-31+G(d) theoretical calculation, revealing the O3H center dot center dot center dot O5 intramolecular hydrogen bonds could remain in the ICs. This work clarified the interactions in cellulose/NaOH/urea aqueous solution and the 3D structure of the cellulose chain in dilute cellulose/NaOH/urea aqueous solution.
引用
收藏
页码:10250 / 10257
页数:8
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