Unusual chirality transfer from silica to metallic nanoparticles with formation of distorted atomic array in crystal lattice structure

Abstract

Transfer of chirality from chiral organic molecules to metallic nanoparticles (NPs) is a very attractive field of research and some unique approaches to obtaining chiral metallic NPs have been developed. However, to date, there has been no report in the literature that the chiral information of silica can be transferred into metallic NPs. In this work, a new chirality transfer system to metallic NPs from chiral silica has been achieved. The chiral transfer was performed by simple two steps: (1) trapping metal cations of silver (Ag) and gold (Au) in chiral silica of nano fibrous bundles embedding poly(ethyleneimine) inside and (2) thermoreducing the metal ions into metallic NPs. The metallic NPs of Au and Ag grown around a silica frame, using a thermo-reduction (calcination) process, showed a spherical shape with a size of about 30 nm. Interestingly, the metallic NPs detached or isolated from the silica via crushing and/or hydrolysis of the silica showed remarkable circular dichroism activity in their plasmon absorption band with an exciton coupling feature. Using an atomic resolution scanning transmission protocol, it was found that the chiral metallic NPs have a definite distortion in the atomic array in their crystal lattice structures. In comparison, achiral metallic NPs, which were prepared using a similar method around achiral silica bundles, showed a precisely ordered atomic line without distortion.