NMR studies of models having the Pt(d(GpG)) 17-membered macrocyclic ring formed in DNA by platinum anticancer drugs: Pt complexes with bulky chiral diamine ligands

The highly distorted Pt(d(G*pG*)) (G* = N7-platinated G) 17-membered macrocyclic ring formed by cisplatin anticancer drug binding to DNA alters the structure of the G*G* base pair steps, canting one base, and increases dynamic motion, complicating solution structural studies. However, the ring appears to favor the HH1 conformation (HH1 denotes head-to-head guanine bases, 1 denotes the normal direction of backbone propagation). Compared to cisplatin, analogues with NH groups in the carrier ligand replaced by bulky N-alkyl groups are more toxic and less active and form less dynamic adducts. To examine the molecular origins for the biological effects of steric bulk, we evaluate Me(4)DABPt(d(G*pG*)) models; the bulk and chirality of Me(4)DAB (N,N,N',N'-tetramethyl-2,3-diaminobutane with S,S or R,R configurations at the chelate ring carbons) impede dynamic motion and enhance the utility of NMR methods for identifying and characterizing conformers. Unlike past studies of adducts with such bulky carrier ligands, in which no HH conformer was found, the Me(4)DABPt(d(G*pG*)) adducts did form the HH1 conformer, providing compelling evidence that the sugar-phosphate backbone can impose constraints sufficient to overcome the alkyl-group steric effects. The HH1 conformer exhibits no significant canting. The (S,S)-Me(4)DABPt(d(G*pG*)) adduct has the least amount of the "normal" HH1 conformer and the greatest amount of the ΔHT1 conformer (ΔHT1 = head-to-tail G* bases with Δ chirality) ever observed (88% under some conditions). Thus, our results lead us to hypothesize that the low activity and high toxicity of analogues of cisplatin having carrier ligands with N-alkyl groups arise from the low abundance and minimal canting of the HH1 conformer and possibly from the adverse effects of an abundant ΔHT1 conformer. The new findings advance our understanding of the chemistry of the Pt(d(G*pG*)) macrocyclic ring and of the effects of carrier-ligand steric bulk on the properties of the ring.     

Linking the historical and chemical definitions of diabatic states for charge and excitation energy transfer reactions in condensed phase

Marcus theory of electron transfer (ET) and Fo?rster theory of excitation energy transfer (EET) rely on the Condon approximation and the theoretical availability of initial and final states of ET and EET reactions, often called diabatic states. Recently [Subotnik et al., J. Chem. Phys. 130, 234102 (2009)], diabatic states for practical calculations of ET and EET reactions were defined in terms of their interactions with the surrounding environment. However, from a purely theoretical standpoint, the definition of diabatic states must arise from the minimization of the dynamic couplings between the trial diabatic states. In this work, we show that if the Condon approximation is valid, then a minimization of the derived dynamic couplings leads to corresponding diabatic states for ET reactions taking place in solution by diagonalization of the dipole moment matrix, which is equivalent to a Boys localization algorithm; while for EET reactions in solution, diabatic states are found through the Edmiston-Ruedenberg localization algorithm. In the derivation, we find interesting expressions for the environmental contribution to the dynamic coupling of the adiabatic states in condensed-phase processes. In one of the cases considered, we find that such a contribution is trivially evaluable as a scalar product of the transition dipole moment with a quantity directly derivable from the geometry arrangement of the nuclei in the molecular environment. Possibly, this has applications in the evaluation of dynamic couplings for large scale simulations.     

On site validation of sound absorption measurements of occupied pews

Laboratory measurements of sound absorption by audiences are known to be scarcely reliable when applied to actual rooms as a consequence of several problems, among which the different area of the “sample” and the different distribution of the reflected sound may play important roles. When dealing with worship places, characterized by a variable degree of occupation and much lower absorption due to unoccupied seats, things become more complicated as absorption seems to be proportional to the number of occupants rather than to the area they cover (as normally accepted in performing spaces). The combination of these variables has been investigated by taking advantage of laboratory measurements and analysing their application to six churches, where on site measurements of reverberation time were carried out with and without occupation. The results are discussed both in terms of simple prediction formulae (Sabine, Eyring, and Arau-Purchades) and of computer simulations, showing that laboratory measurements may be reliably used in computer simulations (at least in the frequency range from 500 Hz on). At low frequencies greater attention must be paid as the absorption coefficients need to be corrected as a function of the actual distribution of the sound field in the room.     

A dimensional split preconditioner for Stokes and linearized Navier-Stokes equations

In this paper we introduce a new preconditioner for linear systems of saddle point type arising from the numerical solution of the Navier-Stokes equations. Our approach is based on a dimensional splitting of the problem along the components of the velocity field, resulting in a convergent fixed-point iteration. The basic iteration is accelerated by a Krylov subspace method like restarted GMRES. The corresponding preconditioner requires at each iteration the solution of a set of discrete scalar elliptic equations, one for each component of the velocity field. Numerical experiments illustrating the convergence behavior for different finite element discretizations of Stokes and Oseen problems are included.     

Are there sterile neutrinos at the eV scale?

New predictions for the antineutrino flux from nuclear reactors suggest that reactor experiments may have measured a deficit in this flux, which can be interpreted in terms of oscillations between the known active neutrinos and new sterile states. We perform a reanalysis of global short-baseline neutrino oscillation data in a framework with one or two sterile neutrinos. While one sterile neutrino is still not sufficient to reconcile the signals suggested by reactor experiments and by the LSND and MiniBooNE experiments with null results from other searches, we find that, with the new reactor flux prediction, the global fit improves considerably when two sterile neutrinos are introduced.     

Intercalant and intermolecular phonon assisted superconductivity in K-doped picene

K(3) picene is a superconducting molecular crystal with a critical temperature of T(c) = 7 or 18 K, depending on the preparation conditions. Using density functional theory we show that electron-phonon interaction accounts for T(c) 3-8 K. The average electron-phonon coupling, calculated by including the phonon energy scale in the electron-phonon scattering, is λ = 0.73 and ω(log) = 18.0 meV. Intercalant and intermolecular phonon modes contribute substantially (40%) to λ as also shown by the isotope exponents of potassium (0.19) and carbon (0.31). The relevance of these modes makes superconductivity in K-doped picene peculiar and different from that of fullerenes.     

Hydrogen oxidation reaction at the Ni/YSZ anode of solid oxide fuel cells from first principles

By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.     

PA66/PA12/clay based nanocomposites: structure and thermal properties

In a previous paper the structure and the physical properties of melt mixed polyamide 66 (PA66)/polyamide 12 (PA12) blends characterized by different compositions have been investigated by means of morphological and physical analyses. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) was introduced in order to evaluate its effect on blends structure and components miscibility. This paper completes the characterization of these materials investigating their thermal properties by means of standard and modulated differential scanning calorimetry (DSC, MDSC), dynamic‐mechanical analysis (DMA), and thermogravimetric analysis (TGA). The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed by analyzing the glass transition temperature (T_g) dependence on composition as well as the existence of strong segmental interactions between polymer components. A compatibilizing action of OMLS has been observed because of a lowering of interfacial tension avoiding coalescence phenomena between particles during melt mixing process. Copyright © 2010 John Wiley & Sons, Ltd.     

Protein adsorption on poly(N-isopropylacrylamide) brushes: dependence on grafting density and chain collapse

The protein resistance of poly(N-isopropylacrylamide) brushes grafted from silicon wafers was investigated as a function of the chain molecular weight, grafting density, and temperature. Above the lower critical solution temperature (LCST) of 32 °C, the collapse of the water-swollen chains, determined by ellipsometry, depends on the grafting density and molecular weight. Ellipsometry, radio assay, and fluorescence imaging demonstrated that, below the lower critical solution temperature, the brushes repel protein as effectively as oligoethylene oxide-terminated monolayers. Above 32 °C, very low levels of protein adsorb on densely grafted brushes, and the amounts of adsorbed protein increase with decreasing brush-grafting-densities. Brushes that do not exhibit a collapse transition also bind protein, even though the chains remain extended above the LCST. These findings suggest possible mechanisms underlying protein interactions with end-grafted poly(N-isopropyl acrylamide) brushes.