Chiral SiO2 and Ag@SiO2 Materials Templated by Complexes Consisting of Comblike Polyethyleneimine and Tartaric Acid.
A facile avenue to fabricate micrometer-sized chiral (L-, D-) and meso-like (dl-) SiO2 materials with unique structures by using crystalline complexes (cPEI/tart), composed of comblike polyethyleneimine (cPEI) and L-, D-, or dl-tartaric acid, respectively, as catalytic templates is reported. Interestingly, both chiral crystalline complexes appeared as regularly left- and right-twisted bundle structures about 10 μm in length and about 5 μm in diameter, whereas the dl-form occurred as circular structures with about 10 μm diameter. Subsequently, SiO2 @cPEI/tart hybrids with high silica content (>55.0 wt %) were prepared by stirring a mixture containing tetramethoxysilane (TMOS) and the aggregates of the crystalline complexes in water. The chiral SiO2 hybrids and calcined chiral SiO2 showed very strong CD signals and a nanofiber-based morphology on their surface, whereas dl-SiO2 showed no CD activity and a nanosheet-packed disklike shape. Furthermore, metallic silver nanoparticles (Ag NPs) were encapsulated in each silica hybrid to obtain chiral (D and L forms) and meso-like (dl form) Ag@SiO2 composites. Also, the reaction between L-cysteine (Lcys) and these Ag@SiO2 composites was preliminarily investigated. Only chiral L- and D-Ag@SiO2 composites promoted the reaction between Lcys and Ag NPs to produce a molecular [Ag-Lcys]n complex with remarkable exciton chirality, whereas the reaction hardly occurred in the case of meso-like (dl-) Ag@SiO2 composite.
Department of Material and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686 (Japan).
Dong-Dong
DD
Yao
Department of Material and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686 (Japan).
Hiroki
H
Murata
Department of Material and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686 (Japan).
Seiji
S
Tsunega
Department of Material and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686 (Japan). rhjin@kanagawa-u.ac.jp.
Ren-Hua
RH
Jin
chirality; polymers; silica; supramolecular chemistry; template synthesis