Computation-led design of pollutant gas sensors with bare and carbon nanotube supported rhodium alloys

Quantum chemical study has been performed on finite-sized bi-metallic Rh3M alloys, M = Ag, Ir, Pd, Pt, Au, derived from magic cluster, Rh4. Bond length of C–O and N–O are noticed to be elongated in the presence of rhodium alloy clusters. CO2 and NO2 gases are found to be highly adsorbed on Rh3M clusters, which is confirmed by stretching frequency of C–O and N–O. DFT evaluated dipole moment and electronic charge redistribution suggests the sensing capability of CO2 and NO2 gases by Rh3M clusters which is further confirmed by the calculated HOMO–LUMO gap. Mixed rhodium alloy clusters supported on single-wall carbon nanotube (SWCNT) exhibits much higher ability to sense CO2 and NO2. On the other hand, SWCNT@Rh3M shows higher catalytic activity for the activation of CO2 and NO2 in comparison to bare Rh3M because of the higher electronic charge redistribution in the case of SWCNT@Rh3M. In case of SWCNT-supported gas adsorbed clusters, p electrons play a major role in bonding.     

Highly Mesoporous Metal‐Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

Effect of guest-host interaction on the dynamics of ethylene glycol in H-ZSM5 zeolite

Dynamics of ethylene glycol (EG) adsorbed in H-ZSM5 zeolite as studied using quasielastic neutron scattering (QENS) technique is reported here. Analysis of QENS data revealed that observed dynamics correspond to isotropic rotational motion of EG. Rotational diffusion coefficient of EG adsorbed in H-ZSM5 zeolite is found to be slower compared to bulk and comparable to that of benzene adsorbed in the same host. Positron Annihilation Spectroscopy (PAS) technique is used to understand the nature of guest-host interaction and the results of both QENS and PAS are found to be consistent with each other.     

Determination of thallium in water samples

This article illustrates the developments of effective preconcentration techniques and highly sensitive detection methods for accurate measurements of Tl species at extremely low concentration in aqueous solutions. The literature on this topic was taken from the Analytical Abstracts in the period 1990-2005.     

Effect of structural misalignments on the temperature variation of basal plane electrical conductivity of graphite

The amount and extent of structural misaligments in natural graphite crystals have been determined, and the temperature variation of the basal plane electrical conductivity (σ_⊥) of naturally occurring graphite has also been studied from 300 to 90 K. The conductivity (σ_⊥) has been found to obey a law σ_⊥α($\text{1}\text{T}$) down to a certain temperature θ (θ varying from sample to sample), below which the variation deviates from linearity towards lower values of σ_⊥. This behaviour, which was earlier thought to be a characteristic of graphite and whose origin could not be traced, has been shown to be an effect of the structural misalignments usually present in natural samples of graphite.     

Effects on mass transfer of atomization and dispersion of liquids in the presence of ultrasound

By applying ultrasound at different frequencies and intensities through the bottom of a narrow tube containing liquids of varying physical properties, followed by critical analysis of the experimental data, a systematic study of the effect of these parameters on enhancement in rate of mass transfer has been made and a correlation has been proposed for prediction of such enhancement.     

Parity-violating electron deuteron scattering and the proton's neutral weak axial vector form factor

We report on a new measurement of the parity-violating asymmetry in quasielastic electron scattering from the deuteron at backward angles at Q2=0.038 (GeV/c)2. This quantity provides a determination of the neutral weak axial vector form factor of the nucleon, which can potentially receive large electroweak corrections. The measured asymmetry A=-3.51+/-0.57 (stat)+/-0.58 (syst) ppm is consistent with theoretical predictions. We also report on updated results of the previous experiment at Q2=0.091 (GeV/c)2, which are also consistent with theoretical predictions.     

Medium-dependent electron and H atom transfer between 2'-deoxyadenosine and menadione: a magnetic field effect study

The interaction between 2'-deoxyadenosine and the model antitumor drug menadione has been studied in organic solvent and in micellar medium. The aim of the work is to elucidate the mechanism of this drug-nucleoside interaction and to determine the environmental effects. Laser flash photolysis and magnetic field effect are used to detect the transients and their spin states. The results indicate that H atom transfer and electron transfer are the operative mechanisms depending upon the medium.