Self-consistent calculation of 1s2s3S state of helium and heliumlike ions

In this paper we present a simple method within the coupled Hartree–Fock framework to calculate the 1s2s ³S state of helium and heliumlike ions. The results are in very good agreement with those obtained by the use of multiterm correlated wave functions. Some interesting observations associated with the wave function are presented.     

Kinetics and mechanism of the oxidation of some neutralized α-Hydroxy acids by hexachloroiridate(IV)

Summary The kinetics of oxidation of some neutralized -hydroxy acids such as lactic (LA), mandelic (MA), -hydroxyisobutyric (IB) and benzilic (BA) acid by hexachloroiridate(IV) have been studied. The oxidation products are acetaldehyde, benzaldehyde, acetone and benzophenone for the respective reactions, which are first order with respect to each substrate and to iridium(IV). The reaction rate increases with increase in pH and salt concentrations. The temperature influence is quite marked in all these reactions. A mechanism involving the formation of an unstable complex, which decomposesvia a free radical pathway to give the respective reaction products, is proposed.     

Selectivity engineered phase transfer catalysis in the synthesis of fine chemicals: reactions of p-chloronitrobenzene with sodium sulphide

Synthesis of chemicals from the same starting material wherein more than one step involving complex reactions are involved can be engineered to produce selectively the desired product by minimising both the by-product formation and separation stages. Several products of industrial importance can be produced from the same starting material by choosing proper conditions and nature and number of phases. The reduction of p-chloronitrobenzene with sodium sulphide was investigated in detail under different modes of phase transfer catalysis (PTC), such as liquid-liquid (L-L), liquid-solid (L-S reaction), and liquid-liquid-liquid (L-L-L) processes. This selectivity engineered PTC reaction has been investigated from mechanistic viewpoint and the rationale of selectivity is delineated.     

Multistage electrophoresis system for the separation of cells, particles and solutes

It is common to operate equilibrium-based separation methods, such as distillation and extraction, as multistage unit operations, in which equilibrium is presumably achieved within each stage. Two rate-based separation processes, free electrophoresis and magnetic particle separation, have now been operated in multistage mode. Preparative free electrophoresis of particles and solutes has resisted scale-up and is confined to a narrow range of ionic compositions. Natural convection induced in electrophoresis buffers by Ohmic heating has been a strong deterrent and has led to such measures as radial electrophoresis in Couette flow, free-flow electrophoresis, low-gravity electrophoresis, density gradient electrophoresis, and reorienting density gradient electrophoresis, to name a few. The short vertical electrophoresis path exploited in the last-mentioned forms the basis for multistage electrophoresis. A thin-layer countercurrent distribution apparatus was designed and constructed so that up to 20 fractions could be collected on the basis of electrophoretic mobility by applying an electric field. The mixture to be separated starts in a bottom cavity, and successive top cavities collect fractions as separand particles or molecules are electrophoresed upward out of the bottom cavity. Mathematical models of this process were developed, and experiments were performed to verify the predictions of the models by collecting and counting particles in each cavity after fractionation.     

Bis-oxalatobisfluoro-aluminates and -gallates

The preparations of some bisoxalatobisfluoroaluminates having the general formula M₃[Al(C₂O₄)₂F₂.3H₂O], where M=K⁺, Na⁺ and [Co(NH₃)₆]³⁺, and a bisoxalatobisfluorogallate, [Co(NH₃)₆] [Ga(C₂O₄)₂F₂].3H₂O, are described. The compounds are characterised by chemical analyses, TGA, IR spectroscopy and X-ray powder photography. IR spectra support the presence of chelating oxalate ligands in these compounds. On isothermal heating at 100–130°C the compounds yield their respective anhydrous products.     

Complex Carbonates of Iron(III)

The complex carbonates of iron(III) are shown to be anionic in nature. The solutions containing these complexes show a maximum absorbance at 460 nm. The complex carbonates of iron(III), viz., (i) K₆[Fe₂(OH)₂(CO₃)₅] · H₂O, — (ii) Na₂[Fe₃O₂(OH)₃(CO₃)₂], — (iii) K[Co(NH₃)₆]₂[Fe₃(OH)₄(CO₃)₆], — (iv) K₅[Co(NH₃)₆]₃[Fe₃(OH) ₄(CO₃)₆]₂, — (v) K[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃], and (vi) NH₄[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃] are isolated and studied by thermogravimetry. The infrared spectra of these compounds are recorded and probable band assignments made. Besides, the reaction between KHCO₃ and Fe(NO₃)₃ was studied through chemical and physicochemical methods.     

Quantum analogue of the Kolmogorov–Arnold–Moser transition in different quantum anharmonic oscillators

The results of numerical computations are presented for the Bohmian trajectories of the family of different one‐ and two‐dimensional anharmonic oscillators, which exhibit regular or chaotic motion in both classical and quantum domains, depending on the values of the parameters appearing in the respective Hamiltonians. Quantum signatures of the Kolmogorov–Arnold–Moser (KAM) transition from the regular to chaotic classical dynamics of these oscillators are studied using a quantum theory of motion (QTM) as developed by de Broglie and Bohm. A phase space distance function between two initially close Bohmian trajectories, the associated Kolmogorov–Sinai–Lyapunov (KSL) entropy, the phase space volume, the autocorrelation function, the associated power spectrum, and the nearest‐neighbor spacing distribution, clearly differentiate the quantum analogues of the corresponding regular and chaotic motions in the classical domain. These quantum anharmonic oscillators are known to be useful in several diverse branches of science. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Application of the lag-after-pulsed-separation (LAPS) flow meter to different protein solutions

A lag after pulsed separation (LAPS) meter was previously developed to measure flow rates of protein solutions. The LAPS meter operates on the time-of-flight principle. An upstream event (electrophoretic concentration of the particles in one section of the device) is detected downstream (by change in ac resistance). The time lag between the event and its detection is inversely proportional to the fluid flow rate. We demonstrate the ability of the LAPS meter to measure the flow rate of solutions containing one or more charged biomacromolecules or particles. A prototype of the LAPS meter was used to measure flow rates of solutions of model proteins [bovine serum albumin (BSA), lysozyme and hemoglobin] and mixtures of BSA and lysozyme. Flow rates of 10-50 microl min(-1)(average velocities of 0.24-1.2 mm s(-1)) were measured. When a single ac measurement was used, the results were solution-dependent, which we attribute to the interface between the protein solution and the ac electrodes. A differential mode, in which the signal from a positive and a negative dc pulse were subtracted from each other, eliminated interfacial effects and led to a single universal (solution-independent) calibration curve. The LAPS meter can be used as a non-invasive, no-moving-parts flow sensor in any microfluidic system (such as drug delivery devices or micro-reactor arrays) where one needs to measure the flow rate of a solution or a suspension containing charged species such as proteins or cells.     

A study of dynamic quadrupolar and octupolar excitations and calculations on excited d and f states of atom and ions: He-sequence

The quadrupolar and octupolar distortion of the ions in the He-sequence caused by an external electro–magnetic field has been studied by a variation–perturbation method in the Hartree–Fock scheme. For certain frequencies singularities appear in the response of the system to the perturbation. Approximate representations for the excited d and f states have been obtained from a study of these resonances. Such a perturbation calculation has the advantage that representations of the different excited states are obtained independently. The orthogonality to all the lower lying levels of the same symmetry is not required. The only source of inaccuracy implicit in the procedure lies in the improper consideration of the inter-electronic interaction. This is corrected for by an independent calculation, which is again formulated in terms of a perturbation treatment. The resulting wave functions for the excited states are accurate in the Hartree–Fock model. Expectation values of several operators have been calculated with these corrected wave functions.     

Probing the association behavior of poly(ethylene glycol)-based amphiphilic comb-like polymer in NaCl solution

The effect of salt on the associative behavior of intramolecular aggregates obtained from poly(ethylene glycol)-based amphiphilic comb-like polymers in aqueous medium at pH 6.2 has been investigated by surface tension, fluorescence probe, dynamic light-scattering, and viscometry techniques. Results reveal that the addition of salt screens the electrostatic repulsion between the charges along the polymer backbone in the aggregates and consequently (1) reduces the surface activity at the air/water interface, (2) leads to the contraction of the polymer backbone, and (3) reduces the hydrodynamic sizes of the aggregates. In contrast, the hydrophobicity of the aggregates remains unperturbed.