Liang Po, Shen Qiang, Zhao Ying, Zhou Yong, Wei Hao, Lieberwirth Ingo, Huang Yaping, Wang Dujin, Xu Duanfu
State Key Laboratory of Polymer Physics and Chemistry, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.
Langmuir. 2004 Nov 23;20(24):10444-8. doi: 10.1021/la0481602.
This paper presents the crystallization behavior of calcium carbonate at the air/liquid interface of aqueous systems of carboxymethyl chitosan (CMCS) using the Kitano method. Although the synthesized CMCS (Mw approximately 100,000) with 1.57 degree of carboxymethyl substitution shows no surface activity, it controls the crystallization of calcium carbonate to form a petunia-shaped superstructure. The shuttlecock-like head of this superstructure strongly supports Colfen's opinion (Rudloff, J.; Colfen, H. Langmuir 2004, 20, 991-996) for the existence of a gas template of CO2 bubbles temporarily captured by polymer molecules, while formation of the stem of this superstructure is provisionally attributed to the presence of the strong electrostatic interactions between calcium ions and the carboxylate groups. The CaCO3 superstructure and its morphology depend not only on the polymer concentration but also on the combined number of calcium ions per CMCS molecule. These results imply that this simple and versatile method expands the morphological investigation of mineralization processes.
本文采用北野法，研究了羧甲基壳聚糖（CMCS）水体系气/液界面处碳酸钙的结晶行为。尽管合成的羧甲基取代度为1.57的CMCS（Mw约为100,000）没有表面活性，但它能控制碳酸钙的结晶，形成矮牵牛形状的超结构。这种超结构的羽毛球状头部有力地支持了科尔芬的观点（Rudloff, J.; Colfen, H. Langmuir 2004, 20, 991 - 996），即聚合物分子暂时捕获的CO2气泡存在气体模板，而这种超结构茎部的形成暂时归因于钙离子与羧酸根基团之间存在强静电相互作用。CaCO3超结构及其形态不仅取决于聚合物浓度，还取决于每个CMCS分子结合的钙离子数量。这些结果表明，这种简单通用的方法扩展了矿化过程的形态学研究。
