Qiu Huibin, Che Shunai
School of Chemistry and Chemical Technology, State Key Laboratory of Composite Materials, Shanghai Jiao Tong University, Shanghai, P. R. China.
J Phys Chem B. 2008 Aug 28;112(34):10466-74. doi: 10.1021/jp802615z. Epub 2008 Jul 31.
A series of achiral cationic and anionic amphiphiles employed as templates for mesoporous silica, all showed an excellent ability to form highly ordered helical mesoporous silica (HMS) crystals. It was supposed that the helical mesostructure may originate from the helical propeller-like micelle formed by the achiral amphiphilic molecules due to their instantaneous asymmetric shape survived in the micelle. The existence of the mirror-imaged conformations of equal proportion may result in the racemic nature of the achiral amphiphile-templated HMSs. The helicity of the HMS greatly depends on the templating molecules which may be modulated by the twisting power of the helical propeller-like packing of the amphiphiles in the micelle. The dependence of the pitch length on different factors was explained by mechanical analysis indicating that the pitch length should be in direct proportion to the rod diameter but inversely proportional to the moment of micelle (M0). Additionally, chiral amphiphiles with opposite charge were used as chiral dopants to control the enantiopurity of the achiral amphiphile-templated HMSs. The absolute enantiomeric excess (ee) of the HMSs increased with increasing amounts of dopant.
一系列用作介孔二氧化硅模板的非手性阳离子和阴离子两亲物,均表现出形成高度有序螺旋介孔二氧化硅(HMS)晶体的出色能力。据推测,螺旋介观结构可能源于非手性两亲分子形成的螺旋桨状胶束,这是由于它们在胶束中存在瞬间不对称形状。等量镜像构象的存在可能导致非手性两亲物模板化HMS的外消旋性质。HMS的螺旋度很大程度上取决于模板分子,而模板分子可能会受到两亲物在胶束中螺旋桨状堆积的扭曲力的调节。通过力学分析解释了螺距长度对不同因素的依赖性,表明螺距长度应与棒直径成正比,但与胶束矩(M0)成反比。此外,使用带相反电荷的手性两亲物作为手性掺杂剂来控制非手性两亲物模板化HMS的对映体纯度。HMS的绝对对映体过量(ee)随着掺杂剂用量的增加而增加。