Ultrasonic and Thermophysical Properties of Cobalt Nanowires

Acoustical Physics - We have estimated elastic, mechanical, thermal and ultrasonic properties, in high temperature regime, of cobalt nanowires (Co-NWs) having a hexagonal close-packed (HCP)...     

On further application of r as a metric for validation of QSAR models

Validation is a crucial aspect for quantitative structure–activity relationship (QSAR) model development. External validation is considered, in general, as the most conclusive proof of predictive capacity of a QSAR model. In the absence of truly external data set, external validation is usually performed on test set compounds, which are members of the original data set but not used in model development exercise. In the case of small data sets, QSAR researchers experience problem in model development due to the fact that the developed models may be less reliable on account of the small number of training set compounds and such models may also show poor external predictability because the models may not have captured all necessary features required for the particular structure–activity relationships. The present paper attempts to show that ‘true r_(LOO)’ statistic calculated based on the model derived from the undivided data set with application of variable selection strategy at each cycle of leave‐one‐out (LOO) validation may reflect external validation characteristics of the developed model thus obviating the requirement of splitting of the data set into training and test sets. This approach may be helpful in the case of small data sets as it uses all available data for model development and validation thus making the resulting model more reliable. Copyright © 2009 John Wiley & Sons, Ltd.     

Hydrogen bonding versus van der Waals interactions: competitive influence of noncovalent interactions on 2D self-assembly at the liquid-solid interface

The structures of the self-assembled monolayers of various 4-alkoxybenzoic acids physisorbed at the liquid-solid interface were established by employing scanning tunnelling microscopy (STM). This study has been essentially undertaken to explore the competitive influence of van der Waals and hydrogen-bonding interactions on the process of two-dimensional self-assembly. These acid derivatives form hydrogen-bonded dimers as expected; however, the dimers organise themselves in the form of relatively complex lamellae. The characteristic feature of these lamellae is the presence of regular discommensurations or kinks along the lamella propagation direction. The formation of kinked lamellae is discussed in light of the registry mechanism of the alkyl chains with the underlying graphite substrate. The location of the kinks along a lamella depends on the number (odd or even) of carbon atoms in the alkyl chain. This result indicates that concerted van der Waals interactions of the alkyl chain units introduce the odd/even chain-length effect on the surface-assembled supramolecular patterns. The odd/even effects are retained even upon complexation with a hydrogen-bond acceptor. However, as the solvent is changed from 1-phenyloctane to 1-octanoic acid, the kinked lamellae as well as the odd/even effects disappear. This solvent-induced convergence of supramolecular patterns is attained by means of co-crystallisation of octanoic acid molecules in the 2D crystal lattice, which is evident from high-resolution STM images. The solvent co-adsorption phenomenon is discussed in terms of competing van der Waals and hydrogen-bonding interactions.     

The allylic nucleophilic substitution of Morita-Baylis-Hillman acetates with isocyanides: a facile synthesis of trisubstituted olefins

Morita-Baylis-Hillman acetates undergo smooth allylic nucleophilic substitution (S_N2′) with tosylmethyl isocyanide (TosMIC) in the presence of a catalytic amount of BF₃·OEt₂ under mild conditions to furnish trisubstituted olefins in high yields with (E)-stereoselectivity.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.     

Quantitative evaluation of benzene, toluene, and xylene in the larvae of Drosophila melanogaster by solid-phase microextraction/gas chromatography/mass spectrometry for potential use in toxicological studies

A simple, rapid, and solvent-free method for quantitative determination of benzene, toluene, and Xylene in exposed Drosophila larvae was developed using headspace solid-phase microextraction (HS-SPME) coupled to GC/MS. Larvae fed on standard Drosophila food mixed with benzene, toluene, and Xylene for 48 h were homogenized in Milli-Q water. Extraction of benzene, toluene, and Xylene was performed at 65 degrees C for 30 min on the SPME fiber (silica-fused). Subsequently, the fiber was desorbed in the GC injection port, followed by GC/MS analysis in the selected-ion monitoring mode. An external calibration curve was used for the quantification of benzene, toluene, and Xylene in the exposed organism. Recoveries were in the range of 78-82% (intraday) and 76-81% (interday) in larvae, and 91-96% (intraday) and 87-92% (interday) in the diet. LOD with an S/N of 3:1 and LOQ with an S/N of 10:1 were in the range of 0.01-0.023 and 0.034-0.077 microg/L, respectively. Percent RSD values for benzene, toluene, and Xylene were in the range of 0.50-0.81 (intraday) and 0.89-1.23 (interday) for retention time, and 2.16--3.85 (intraday) and 2.99-4.95 (interday) for peak concentration, showing good repeatability. This method was sensitive enough to quantitate benzene, toluene, and Xylene in small exposed organisms like Drosophila larvae. The SPME/GC/MS method developed may have wider applications in various in vivo toxicological studies.     

Fast compressional wave attenuation and dispersion due to conversion scattering into slow shear waves in randomly heterogeneous porous media

Within the viscosity-extended Biot framework of wave propagation in porous media, the existence of a slow shear wave mode with non-vanishing velocity is predicted. It is a highly diffusive shear mode wherein the two constituent phases essentially undergo out-of-phase shear motions (slow shear wave). In order to elucidate the interaction of this wave mode with propagating wave fields in an inhomogeneous medium the process of conversion scattering from fast compressional waves into slow shear waves is analyzed using the method of statistical smoothing in randomly heterogeneous poroelastic media. The result is a complex wave number of a coherent plane compressional wave propagating in a dynamic-equivalent homogeneous medium. Analysis of the results shows that the conversion scattering process draws energy from the propagating wave and therefore leads to attenuation and phase velocity dispersion. Attenuation and dispersion characteristics are typical for a relaxation process, in this case shear stress relaxation. The mechanism of conversion scattering into the slow shear wave is associated with the development of viscous boundary layers in the transition from the viscosity-dominated to inertial regime in a macroscopically homogeneous poroelastic solid.     

Micellization of a cationic gemini surfactant in aqueous solutions with different alkanols and alkanediols as additives: Effect of nonpolar chain and position of hydroxyl groups

The gemini surfactant N-N′bis(dimethyldodecyl)-1,4-butanediammonium dibromide (12-4-12) was synthesized and its critical micelle concentrations (CMCs) and degree of counterion dissociation (α) in aqueous solutions in the presence of alkanols viz ethanol, isomeric butyl alcohols, 1-hexanol and alkanediols (ethanediol, 1,4-butanediol, 1,2-hexanediol, 2,5-hexanediol 1,6-hexanediol, and 1,8-octanediol) determined from electrical conductivity are reported. While ethanol, ethanediol, 1,4-butanediol showed an increase in CMC, a decrease was seen for isomeric butyl alcohols, 1-hexanol, isomeric hexanediols and 1,8-octanediol. For butyl alcohols the CMC decrease showed the trend 1° >2° > 3°; in C₆ diols, 1,2-hexanediol exerted more decrease as compared to 2,5-hexanediol and 1,6-hexanediol.The results are explained on the basis of the structure and hydrophobicity of alcohols that determine their effect as cosolvent or cosurfactant (partitioning in micelles). Two-dimensional nuclear overhauser enhancement spectroscopy (2D-NOESY) was used to examine the location for 1-butanol and 1,4-butanediol in micellar systems as representative additives from alkanols and alkanediols showing CMC decreasing and increasing effect respectively.