title: Electronic structure and UV absorption spectra of metal-mediate DNA: an approach from theoretical chemistry.
abstract: We theoretically evaluated the stability, UV-Vis spectra and possibility of stacking of [S-M(II)-S] (M=Ni, Pd, Pt, S: hydroxypyridonethione) by means of the density functional theory (DFT). From the view of the free energy, we assessed formation energy of possible combinations of chalcogen atoms and metal cations. The results confirmed that [H-Ni(II)-H] and [S-Cu(II)-S] would form stable metal-base pairing, on the other hand [H-Pt(II)-H] would not, which have been experimentally proven. Moreover, by use of time-dependent density functional theory (TDDFT), we observed d-pi* transition accompanied with pi-pi* transition in [S-M(II)-S]. These results reveal that metal-to-ligand charge transfer (MLCT) shifts the peak of pi-pi* transition in [S-2H(+)-S] (without metal cations).
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan. matsui@chem.sci.osaka-u.ac.jp
authors.forename: Toru
authors.initials: T
authors.lastname: Matsui
authors.forename: Hideaki
authors.initials: H
authors.lastname: Miyachi
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Nakanishi
authors.forename: Yasuteru
authors.initials: Y
authors.lastname: Shigeta
authors.forename: Yasutaka
authors.initials: Y
authors.lastname: Kitagawa
authors.forename: Mitsutaka
authors.initials: M
authors.lastname: Okumura
authors.forename: Kimihiko
authors.initials: K
authors.lastname: Hirao
mesh_terms: D004247:DNA / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D013056:Spectrophotometry, Ultraviolet
chemical_list: D008670:Metals; D004247:DNA