Instabilities in free-surface electroosmotic flows

Instability of a thin electrolyte film undergoing a direct current electroosmotic flow has been investigated. The film with a compliant electrolyte–air interface is flowing over a rigid charged substrate. Unlike previous studies, inclusion of the Maxwell stresses in the formulation shows the presence of a new finite wavenumber shear-flow mode of instability, alongside the more frequently observed long-wave interfacial mode. The shear mode is found to be the dominant mode of instability when the electrolyte–solid and electrolyte–air interfaces are of opposite charge or of same charge but have very large zeta-potential at the electrolyte–air interface. The conditions for mode-switch (interfacial to shear) and the direction of the travelling waves are discussed through stability diagrams. Interestingly, the analysis shows that when the interfaces are of nearly same zeta potential, the ‘free’ electrolyte–air interface behaves more like a ‘stationary’ wall because of the ion transport in the reverse direction of the flow.     

Phonon dispersion in aluminium arsenide and antimonide

The phonon dispersion curves for aluminium arsenide and antimonide have been investigated by using a deformation bond approximation model. The results obtained from this model are compared with the experimental values wherever it is available. Since there is no complete experimental phonon dispersion curves for AlAs, we could not compare our calculated results, but the results of AlSb have been compared with the inelastic neutron scattering measurements at 15 K. However, we compare the phonon frequencies of AlAs and AlSb at critical points of the Brillouin zone obtained by our calculations and Raman spectroscopy measurements. This model predicts the phonon modes satisfactorily in all the symmetry directions of the Brillouin zone (BZ). The spectrum has similar features as observed in other III–V compound semiconductors.     

Lattice vibrational properties of uranium pnictides

Lattice vibrational properties of uranium pnictides have been studied using breathing shell model (BSM) which includes breathing motion of electrons of the U-atoms due tof−d hybridization. The phonon dispersion curves of U-pnicitides calculated from the present model agree reasonably well with the measured data. A comparison has been made between BSM and our results reported earlier obtained from three-body force rigid ion model to reveal the importance of the short-range electron-phonon interactions in these compounds. We also report, for the first time, the two phonon density of states and specific heat for these compounds.     

Kinetics and mechanisms of substitution of aqua-ligands in cis-diaqua-bis(bipyridyl)ruthenium(ll) ion by L-cysteine in aqueous medium

Transition Metal Chemistry - The title reaction has been studied spectrophotometrically and a rate-law established within the pH range 5.0 to 6.5, $$ {?...     

Calibration transfer between electronic nose systems for rapid In situ measurement of pulp and paper industry emissions

Electronic nose systems when deployed in network mesh can effectively provide a low budget and onsite solution for the industrial obnoxious gaseous measurement. For accurate and identical prediction capability by all the electronic nose systems, a reliable calibration transfer model needs to be implemented in order to overcome the inherent sensor array variability. In this work, robust regression (RR) is used for calibration transfer between two electronic nose systems using a Box–Behnken (BB) design. Out of the two electronic nose systems, one was trained using industrial gas samples by four artificial neural network models, for the measurement of obnoxious odours emitted from pulp and paper industries. The emissions constitute mainly of hydrogen sulphide (H₂S), methyl mercaptan (MM), dimethyl sulphide (DMS) and dimethyl disulphide (DMDS) in different proportions. A Box–Behnken design consisting of 27 experiment sets based on synthetic gas combinations of H₂S, MM, DMS and DMDS, were conducted for calibration transfer between two identical electronic nose systems. Identical sensors on both the systems were mapped and the prediction models developed using ANN were then transferred to the second system using BB–RR methodology. The results showed successful transmission of prediction models developed for one system to other system, with the mean absolute error between the actual and predicted concentration of analytes in mg L⁻¹ after calibration transfer (on second system) being 0.076, 0.1801, 0.0329, 0.427 for DMS, DMDS, MM, H₂S respectively.     

Derivatization of Coumarins at the Benzenoid Ring in Aqueous Medium

Some 6‐disubstituted, 8‐disubstituted, and/6,8‐disubstituted compounds have been prepared from coumarin, 7‐methylcoumarin, and 3,4‐benzocoumarin. The Reimer–Tiemann reaction, Lederer–Manasse reaction, bromination using molecular bromine as well as 2,4,4,6‐tetrabromocyclohex‐2,5‐dien‐1‐one, Elbs reaction, and diazocoupling have been carried under controlled conditions to obtain various derivatives. Further, several reactions of aldehyde derivatives of these coumarins have been carried on to prepare important functional compounds including some heterocycles. It is noteworthy that these aldehydes behave as phenolic aldehydes under alkaline conditions to undergo the Dakin reaction. The reactions are mostly carried in aqueous media involving a dianionic intermediate and hence fulfill one important criterion of green chemistry.     

Groebke-Blackburn-Bienaymé multicomponent reaction in scaffold-modification of adenine, guanine, and cytosine: synthesis of aminoimidazole-condensed nucleobases

A multicomponent method for scaffold-modification of nucleobases (adenine, guanine, and cytosine) was developed. This modification approach, as an alternative to usual synthetic routes involving protection-deprotection or S_NAr of halo (or leaving group-equivalent)-purines, affords in one step therapeutically-relevant substituted aminoimidazole-[i]-condensed adenine, [b]-condensed guanine, [c]-condensed cytosine. These derived nucleobases possess enhanced lipophilicity and solubility and contain the functionalities useful for further chemical manipulations.     

Swelling, functionalization, and structural changes of the nanoporous layered silicates AMH-3 and MCM-22

Nanoporous layered silicate materials contain 2D-planar sheets of nanoscopic thickness and ordered porous structure. In comparison to porous 3D-framework materials such as zeolites, they have advantages such as significantly increased surface area and decreased diffusion limitations because the layers can potentially be exfoliated or intercalated into polymers to form nanocomposite materials. These properties are particularly interesting for applications as materials for enhancing molecular selectivity and throughput in composite membranes. In this report, the swelling and surface modification chemistry of two attractive nanoporous layered silicate materials, AMH-3 and MCM-22, were studied. We first describe a method, using long-chain diamines instead of monoamines, for swelling of AMH-3 while preserving its pore structure to a greater extent during the swelling process. Then, we describe a stepwise functionalization method for functionalizing the layer surfaces of AMH-3 and MCM-22 via silane condensation reactions. The covalently attached hydrocarbon chain molecules increased the hydrophobicity of AMH-3 and MCM-22 layer surfaces and therefore allow the possibility of effectively dispersing these materials in polymer matrices for thin film/membrane applications.