RESUMO

The gas-phase structures of cytosine-Ag(+) [CAg](+) and cytosine-Ag(+)-H2O [CAg-H2O](+) complexes have been studied by mass-selected infrared multiphoton dissociation (IRMPD) spectroscopy in the 900-1800 cm(-1) spectral region using the Free Electron Laser facility in Orsay (CLIO). The IRMPD experimental spectra have been compared with the calculated IR absorption spectra of the different low-lying isomers (computed at the DFT level using the B3LYP functional and the 6-311G++(d,p) basis set for C, H, N and O atoms and the Stuttgart effective core potential for Ag). For the [CAg](+) complex, only one isomer with cytosine in the keto-amino (KA) tautomeric form and Ag(+) interacting simultaneously with the C(2)[double bond, length as m-dash]O(7) group and N(3) of cytosine was observed. However, the mono-hydration of the complex in the gas phase leads to the stabilization of a two quasi-isoenergetic structure of the [CAg-H2O](+) complex, in which Ag(+) interacts with the O atom of the water molecule and with the N(3) or C(2)[double bond, length as m-dash]O(7) group of cytosine. The relative populations of the two isomers determined from the IRMPD kinetics plot are in good agreement with the calculated values. Comparison of these results with those of protonated cytosine [CH](+) and its mono-hydrated complex [CH-H2O](+) shows some interesting differences between H(+) and Ag(+). In particular, while a single water molecule catalyzes the isomerization reaction in the case of [CH-H2O](+), it is found that in the case of [CAg-H2O](+) the addition of water leads to the stabilization of two isomers separated by small energy barrier (0.05 eV).

Assuntos

Complexos de Coordenação/química , Citosina/química , Prata/química , Cátions Monovalentes/química , Espectrometria de Massas , Modelos Moleculares , Espectrofotometria Infravermelho , Termodinâmica , Água/química

RESUMO

The study of metal ion-DNA interaction aiming to understand the stabilization of artificial base pairing and a number of noncanonical motifs is of current interest, due to their potential exploitation in developing new technological devices and expanding the genetic code. A successful strategy has been the synthesis of metal-mediated base pairs, in which a coordinative bond to a central metal cation replaces a H-bond in a natural pair. In this work, we characterized, for the first time, the gas phase structure of the cytosine···Ag+···cytosine (C-Ag+-C) complex by means of InfraRed-MultiPhoton-Dissociation (IR-MPD) spectroscopy and theoretical calculation. The IR-spectrum was confidently assigned to one structure with the Ag+ acting as a bridge between the heteronitrogen atoms in each cytosine (both in the keto-amino form). This structure is biologically relevant since it mimics the structure of the hemiprotonated C-H+-C dimer responsible for the stabilization of the i-motif structure in DNA, with the replacement of the NH···N bond by a stronger N···Ag+···N bond. Moreover, since the structure of the C-Ag+-C complex is planar, it allows an optimum intercalation between pairs of the two antiparallel strand duplex in the DNA i-motif structure.