Electron transfer in the reduction of primary halides by metal hydrides

The reactions of various main-group metal hydrides with 1-halo-5-hexenes and with 1-halo-2,2-dlmethyl-5-hexenes produce both straight chain and cyclized reduction products. The formation of cyclic hydrocarbons clearly indicates the presence of radical intermediates during the course of these reactions.     

Statistical properties and kinetics of end-end contact formation of unfolded polypeptides: a systematic molecular dynamics study

The authors have systematically examined the statistical properties of the unfolded states of series of polypeptides and the kinetics of their end-to-end contact (ring closure) formation by molecular dynamics simulations. The formation of an end-to-end contact follows a single-exponential decay as measured by the first-passage time. It is shown that the shifted Gaussian chain model can be applied to describe the dimensions of glycine-rich polypeptides at high temperature. However, notable deviation from the ideal Gaussian chain model was observed at lower temperatures particularly for those polypeptides without glycines, due to the tendency to form local structures.     

Untersuchungen über die diamagnetische Suszeptibilität einiger Organo (imino-oxy)silane

Diamagnetic susceptibilities of trimethyl(imino-oxy)silanes,Me ₃SiON CMeR, and dimethyldi(imino-oxy)silanes,Me ₂Si(ON CMeR)₂, containing Si–O bonds are reported. _M of these silicon compounds has been calculated theoretically from the method ofBaudet et al. and a good agreement has been obtained between the observed _M values and the corresponding calculated values. _Si in these compounds has been calculated graphically and the lower values have been explained on the basis of back-bonding to the silicon atom from the oxygen lone pair.     

Strong Law of Large Numbers for Betti Numbers in the Thermodynamic Regime

Journal of Statistical Physics - We establish the strong law of large numbers for Betti numbers of random ?ech complexes built on $${\mathbb {R}}^N$$ -valued binomial point processes and...     

Electrochemical behavior of different structural states of the alloy Ti60Ni40

Potentiodynamic polarization studies were carried out on nanocrystalline I, nanocrystalline II and nanocrystalline III states having crystallite size 35 ± 5 nm, 18 ± 2 nm and 10 ± 2 nm of the alloy Ti₆₀Ni₄₀ in 1 M H₂SO₄ aqueous medium. It was observed that the nanocrystalline III state exhibits superior corrosion resistance as compared to the nanocrystalline II and nanocrystalline I states of the alloy Ti₆₀Ni₄₀. XPS studies were also performed after corrosion test and it was observed that nanocrystalline III state contains only Ti²⁺ and Ti⁴⁺ species whereas nanocrystalline I and nanocrystalline II state contains Ti²⁺, Ti³⁺and Ti⁴⁺ along with some unoxidized metallic Ti⁰ in the case of nanocrystalline I state. Thus the small crystallite size and the presence of only Ti²⁺ and Ti⁴⁺ species in the form of TiO and TiO₂ leads to the formation of a protective oxide film which is adherent, stable and improves the corrosion resistance of the nanocrystalline III state of the alloy Ti₆₀Ni₄₀.     

Effect of BaO on the crystallization kinetics of glasses along the Diopside-Ca-Tschermak join

We report on the effect of BaO on the crystallization kinetics of glasses in the diopside (CaMgSi₂O₆)-Ca-Tschermak (CaAl₂SiO₆) system. Partial substitution (i.e. 5%, 10% and 20%) of Ba²⁺ for Ca²⁺ was attempted in composition CaMg_0.8Al_0.4Si_1.8O₆, in three different glasses while partial substitution of B³⁺ for Al³⁺ was made in the fourth glass. Structural investigations on the glasses have been made by density measurements, molar volume and Infra-red spectroscopy (FTIR). Non-isothermal crystallization kinetic studies have been employed to study the mechanism of crystallization in all the four glasses. The Avrami parameter for the glass powders is ∼2, indicating the existence of intermediate mechanism of crystallization. Crystallization sequence in the glasses has been followed by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and FTIR. Augite crystallized out being the dominant phase in all the glass-ceramics, while different polymorphs of BaAl₂Si₂O8 were present as secondary or minor phases.     

Herringbone and Helical Self-Assembly of π-Conjugated Molecules in the Solid State through CH/π Hydrogen Bonds

Self-organization of organic molecules through weak noncovalent forces such as CH/π interactions and creation of large hierarchical supramolecular structures in the solid state are at the very early stage of research. The present study reports direct evidence for CH/π interaction driven hierarchical self-assembly in π-conjugated molecules based on custom-designed oligophenylenevinylenes (OPVs) whose structures differ only in the number of carbon atoms in the tails. Single-crystal X-ray structures were resolved for these OPV synthons and the existence of long-range multiple-arm CH/π interactions was revealed in the crystal lattices. Alignment of these π-conjugated OPVs in the solid state was found to be crucial in producing either right-handed herringbone packing in the crystal or left-handed helices in the liquid-crystalline mesophase. Pitch- and roll-angle displacements of OPV chromophores were determined to trace the effect of the molecular inclination on the ordering of hierarchical structures. Furthermore, circular dichroism studies on the OPVs were carried out in the aligned helical structures to prove the existence of molecular self-assembly. Thus, the present strategy opens up new approaches in supramolecular chemistry based on weak CH/π hydrogen bonding, more specifically in π-conjugated materials.     

Size and structure matter: enhanced CO2 photoreduction efficiency by size-resolved ultrafine Pt nanoparticles on TiO2 single crystals

A facile development of highly efficient Pt-TiO(2) nanostructured films via versatile gas-phase deposition methods is described. The films have a unique one-dimensional (1D) structure of TiO(2) single crystals coated with ultrafine Pt nanoparticles (NPs, 0.5-2 nm) and exhibit extremely high CO(2) photoreduction efficiency with selective formation of methane (the maximum CH(4) yield of 1361 μmol/g-cat/h). The fast electron-transfer rate in TiO(2) single crystals and the efficient electron-hole separation by the Pt NPs were the main reasons attributable for the enhancement, where the size of the Pt NPs and the unique 1D structure of TiO(2) single crystals played an important role.     

Bayesian latent variable regression via Gibbs sampling: methodology and practical aspects

Bayesian latent variable regression (BLVR) aims to utilize all available information for empirical modeling via a Bayesian framework. Such information includes prior knowledge about the underlying variables, model parameters and measurement error distributions. This paper improves upon the existing optimization‐based BLVR (BLVR‐OPT) method [1] by developing a sampling‐based Bayesian latent variable regression (BLVR‐S) method that relies on Gibbs sampling. Use of the sampling‐based framework not only provides point estimates, but its ability to generate samples that represent the posterior distribution of the unknown variables, also readily provides error bounds. Features and advantages of this method are demonstrated via examples based on simulated data and real Near‐Infrared (NIR) spectroscopy data. Practical aspects of Bayesian modeling such as determining when the extra computation may be worth the effort are addressed by an empirical study of the effects of the amount of training data and signal to noise ratio (SNR). The benefits of BLVR seem to be most significant when the number of measurements is limited and when noise in output variables is relatively large. Copyright © 2007 John Wiley & Sons, Ltd.