Solution structure of a DNA double helix with consecutive metal-mediated base pairs

Metal-mediated base pairs represent a powerful tool for the site-specific functionlization of nucleic acids with metal ions. The development of applications of the metal-modified nucleic acids will depend on the availability of structural information on these double helices. We present here the NMR solution structure of a self-complementary DNA oligonucleotide with three consecutive imidazole nucleotides in its centre. In the absence of transition-metal ions, a hairpin structure is adopted with the artifical nucleotides forming the loop. In the presence of Ag(I) ions, a duplex comprising three imidazole-Ag+-imidazole base pairs is formed. Direct proof for the formation of metal-mediated base pairs was obtained from (1)J(N-15,Ag-107/109) couplings upon incorporation of N-15-labelled imidazole. The duplex adopts a B-type conformation with only minor deviations in the region of the artifical bases. This work represents the first structural characterization of a metal-modified nucleic acid with a continuous stretch of metal-mediated base pairs

SixC1 12xO2 alloys: A possible route to stabilize carbon-based silica-like solids?

Novel extended tetrahedral forms Of CO2 have been synthesized recently under high-pressure conditions. We perform ab initio density functional theory calculations to investigate whether doping with Si can extend the stability range of such tetrahedral forms Of CO2 to ambient pressure. Calculations are performed with a simple cubic cell containing eight formula units in alpha-cristobalite-like structure. Though we find that all the SiC1-xO2 structures considered by us are thermodynamically unstable with respect to decomposition into the end members at ambient pressures, the energy differences are small, suggesting that it might be possible for such phases to exist in metastable forms. At higher pressures, the heat of formation is found to be negative. The bonding between C and O atoms is more covalent than that between Si and 0 atoms. We also find indications that some C atoms may prefer three-fold coordination at low pressur