title: Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.
abstract: We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT.
authors.affiliation: National Food Research Institute (NFRI), National Agriculture and Food Research Organization (NARO), 2-1-12 Kannondai, Tsukuba, Ibaraki 305-8642, Japan. Electronic address: riwaura@affrc.go.jp.
authors.forename: Rika
authors.initials: R
authors.lastname: Iwaura
authors.affiliation: Department of Chemistry, Faculty of Science, Tokyo University of Science (TUS), 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors.forename: Hiroharu
authors.initials: H
authors.lastname: Yui
authors.affiliation: Department of Chemistry, Faculty of Science, Tokyo University of Science (TUS), 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors.forename: Yuu
authors.initials: Y
authors.lastname: Someya
authors.affiliation: National Food Research Institute (NFRI), National Agriculture and Food Research Organization (NARO), 2-1-12 Kannondai, Tsukuba, Ibaraki 305-8642, Japan.
authors.forename: Mayumi
authors.initials: M
authors.lastname: Ohnishi-Kameyama
mesh_terms: D000873:Anthracenes / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D004735:Energy Transfer; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000873:Anthracenes; D004247:DNA; C034020:anthracene
keywords: Acene; DNA; Energy transfer; Excimer; Nanostructures; Self-assembly