Jin Haiying, Qiu Huibin, Sakamoto Yasuhiro, Shu Peng, Terasaki Osamu, Che Shunai
School of Chemistry and Chemical Technology, State Key Laboratory of Composite Materials, Shanghai Jiao Tong University, Shanghai, China.
Chemistry. 2008;14(21):6413-20. doi: 10.1002/chem.200701988.
Using lipids (N-acyl amino acids) and 3-aminopropyltriethoxysilane as structure- and co-structure-directing agents, mesoporous silicas with four different morphologies, that is, helical ribbon (HR), hollow sphere, circular disk, and helical hexagonal rod, were synthesized just by changing the synthesis temperature from 0 degrees C to 10, 15, or 20 degrees C. The structures were studied by electron microscopy. It was found that 1) the structures have double-layer disordered mesopores in the HR, radially oriented mesopores in the hollow sphere, and highly ordered straight and chiral 2D-hexagonal mesopores in the disklike structure and helical rod, respectively; 2) these four types of mesoporous silica were transformed from the flat bilayered lipid ribbon with a chain-interdigitated layer phase through a solid-solid transformation for HR formation and a dissolving procedure transformation for the synthesis of the hollow sphere, circular disk, and twisted morphologies; 3) the mesoporous silica helical ribbon was exclusively right-handed and the 2D-hexagonal chiral mesoporous silica was excessively left-handed when the L-form N-acyl amino acid was used as the lipid template; 4) the HR was formed only by the chiral lipid molecules, whereas the 2D-hexagonal chiral mesoporous silicas were formed by chiral, achiral, and racemic lipids. Our findings give important information for the understanding of the formation of chiral materials at the molecular level and will facilitate a more efficient and systematic approach to the generation of rationalized chiral libraries.
以脂质(N-酰基氨基酸)和3-氨丙基三乙氧基硅烷作为结构导向剂和共结构导向剂,仅通过将合成温度从0℃改变为10℃、15℃或20℃,就合成了具有四种不同形态的介孔二氧化硅,即螺旋带(HR)、空心球、圆盘和螺旋六角棒。通过电子显微镜对结构进行了研究。发现:1)HR结构具有双层无序介孔,空心球具有径向排列的介孔,盘状结构和螺旋棒分别具有高度有序的直的和手性的二维六方介孔;2)这四种类型的介孔二氧化硅是由具有链交错层相的扁平双层脂质带通过HR形成的固-固转变以及空心球、圆盘和扭曲形态合成的溶解过程转变而来;3)当使用L型N-酰基氨基酸作为脂质模板时,介孔二氧化硅螺旋带完全是右手性的,二维六方手性介孔二氧化硅则是过度左手性的;4)HR仅由手性脂质分子形成,而二维六方手性介孔二氧化硅由手性、非手性和外消旋脂质形成。我们的发现为在分子水平上理解手性材料的形成提供了重要信息,并将促进一种更有效、更系统的方法来生成合理的手性文库。