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Ab initio molecular dynamics simulations of SiO2 in supercritical water at temperatures of 900 K and 1200 K and a pressure of 1.5 GPa at concentrations of 5 wt% and 16 wt% have been carried out. The different polymeric forms SiO4H4, Si2O7H6, and Si3O10H8 are found to be energetically similar within the statistical error, suggesting that all three polymeric forms play an important role in solutions at the above conditions. However, neither spontaneous polymerization nor depolymerization has been observed during the 10-ps time span of the simulations. The dynamic and structural properties of the supercritical solutions have been analyzed in terms of diffusion coefficients, vibrational spectra, and radial pair distribution functions. [ABSTRACT FROM AUTHOR]

A benzothiazole-substituted derivative (X) of 1,3-diaza-2-oxophenoxazine was evaluated with respect to its ability to engage in Ag(I)-mediated homo base pair formation in two different DNA duplexes. The metal binding was determined by a combination of temperature-dependent UV spectroscopy, CD spectroscopy, and fluorescence spectroscopy, indicating the incorporation of two Ag(I) ions to generate a dinuclear X-Ag(I) 2 -X base pair. Interestingly, a luminescence increase was observed upon metal binding. Theoretical luminescence spectra were calculated using time-dependent density functional theory (TDDFT) for all possible Ag(I)-mediated X : X base pair geometries to identify the species responsible for the increase in luminescence. The study shows that even bulky non-planar artificial nucleobases can be applied to form stabilizing metal-mediated base pairs.

Electron attachment to formamide clusters in helium nanodroplets is reported for the first time. In contrast to the gas phase, parent anions are seen following low energy electron attachment to both the monomer and the small clusters. This is attributed to formation of dipole (or quadrupole) bound anions. In addition to the bare anions, the mass spectra also show the monomer and clusters with attached helium atoms. The affinity for attaching helium atoms strongly varies with cluster size; for example, the dimer anion is more than 10 times more likely to bind one or more helium atoms than the monomer. Possible binding sites for the helium atoms are discussed.