title: Water-dependent optical activity inversion of chiral DNA-silica assemblies.
abstract: Chirality is widely found in nature and is expressed hierarchically in many organic-inorganic hybrid materials. Optical activity (OA) is the most fundamental attribute of these chiral materials. In this study, we found that the OA of impeller-like chiral DNA-silica assemblies (CDSAs) was inverted with the addition of water. The state of DNA under dry and wet conditions, and the dual chirality of chiral DNA layers and twisted helical arrays of opposite handedness in CDSAs were considered to exert predominant effects on the OAs. The circular dichroism (CD) responses for the dry CDSAs were mostly attributed to the chiral arrangement of DNA layers, whereas the opposite CD responses for the wet CDSAs primarily originated from twisted helical arrays of DNA molecules. The observed CD signals were a super-position of the two opposing OA responses. The increase in the longitudinal relation of DNA molecules due to the recovery of a double-helical structure of DNA in the presence of water was considered to be the reason for the increase in intensity of the CD signals that originated from the twisted helical array, which led to the inversion of OA of the CDSAs. The inversion of the plasmon-resonance-based OAs for the chiral-arranged achiral Ag nanoparticles (NPs) located in the channels of the CDSAs in dry and wet states further confirmed the dual chirality of DNA packing. Such research on DNA assemblies and metal NPs with dual, opposite chirality assists in the understanding of DNA hierarchical chirality in living systems and the creation of macroscopic ordered helical materials and biosensors.
authors.affiliation: School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 (P.R. China), Fax: (+86) 21-5474-5365.
authors.forename: Ben
authors.initials: B
authors.lastname: Liu
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Cao
authors.forename: Yingying
authors.initials: Y
authors.lastname: Duan
authors.forename: Shunai
authors.initials: S
authors.lastname: Che
mesh_terms: D002942:Circular Dichroism; D004247:DNA / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry; D009904:Optical Rotation; D012822:Silicon Dioxide / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D012834:Silver; D012822:Silicon Dioxide; D004247:DNA
keywords: DNA; chirality; optical activity; organic-inorganic hybrid composites; self-assembly