水中的手性聚（脲基邻苯二甲酰亚胺）折叠体

Chiral poly(ureidophthalimide) foldamers in water.

作者信息

Sinkeldam Renatus W, van Houtem Michel H C J, Pieterse Koen, Vekemans Jef A J M, Meijer E W

机构信息

Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P. O. Box 513, 5600 MB Eindhoven, The Netherlands.

出版信息

Chemistry. 2006 Aug 7;12(23):6129-37. doi: 10.1002/chem.200600476.

DOI:10.1002/chem.200600476

PMID:16795110

Abstract

Poly(ureidophthalimide)s decorated with hydrophilic side chains, that ensure solubility in aqueous media, have been synthesized and characterized by UV/Vis and circular dichroism (CD) spectroscopy. Temperature and concentration dependent CD measurements in water have revealed an almost temperature and concentration independent Cotton effect, indicative for a strong intramolecular organization. Similar studies in THF demonstrate the dynamic nature of the secondary architecture, a characteristic of foldamers. In addition, the bisignated Cotton effect in water is opposite in sign to that in THF, suggestive for a solvent-dependent preference for one helical handedness. Mixing experiments prove the dominance of water in determining the handedness of the helical architecture. The solvent allows for control over the helical architecture and thus governs the supramolecular synthesis.

摘要

已合成了带有亲水性侧链的聚（脲基邻苯二甲酰亚胺），这些侧链确保了其在水性介质中的溶解性，并通过紫外可见光谱和圆二色性（CD）光谱对其进行了表征。在水中进行的温度和浓度依赖性CD测量显示出几乎与温度和浓度无关的科顿效应，这表明存在强烈的分子内组织。在四氢呋喃中进行的类似研究证明了二级结构的动态性质，这是折叠体的一个特征。此外，在水中的双符号科顿效应在符号上与在四氢呋喃中的相反，这表明对一种螺旋手性存在溶剂依赖性偏好。混合实验证明了水在决定螺旋结构手性方面的主导作用。溶剂允许对螺旋结构进行控制，从而支配超分子合成。