Procedure for determination of trace ions in boric acid by matrix volatilization-ion chromatography

A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated.     

Thermodynamic stability of CaThF6(cr) by transpiration and e.m.f. techniques

In the present paper, we report the standard molar Gibbs energy of formation for CaThF₆ measured by gas equilibration and e.m.f. methods. The HF(g) vapour pressure over the equilibrium reaction: \({\text{CaThF}}_{6} \left( {\text{cr}} \right) + 2 {\text{H}}_{ 2} {\text{O}}\left( {\text{g}} \right) = {\text{CaF}}_{2} \left( {\text{cr}} \right) + {\text{ThO}}_{2} \left( {\text{cr}} \right) + 4{\text{HF}}\left( {\text{g}} \right)\) has been measured using transpiration technique. The above reaction mechanism has been established employing TG and XRD techniques. A fluoride e.m.f. cell: (−)Pt, CaF₂(cr) + ThOF₂(cr) + CaThF₆(cr) |CaF₂(cr)| NiO(cr) + NiF₂(cr), Pt(+) has been constructed to measure Gibbs energy of formation of CaThF₆ (cr) using CaF₂ (cr) as a solid electrolyte. The isobaric heat capacity \({\text{Cp}}_{\text{m}}^{{\circ }} \left( T \right)\) of the compound has been measured using differential scanning calorimetric technique. Based on the experimental results, thermodynamic functions for CaThF₆ have been generated.

     

Adsorption of organic molecules on silica surface

The adsorption behaviour of various organic adsorbates on silica surface is reviewed. Most of the structural information on silica is obtained from IR spectral data and from the characteristics of water present at the silica surface. Silica surface is generally embedded with hydroxy groups and ethereal linkages, and hence considered to have a negative charged surface prone to adsorption of electron deficient species. Adsorption isotherms of the adsorbates delineate the nature of binding of the adsorbate with silica. Aromatic compounds are found to involve the pi-cloud in hydrogen bonding with silanol OH group during adsorption. Cationic and nonionic surfactants adsorb on silica surface involving hydrogen bonding. Sometimes, a polar part of the surfactants also contributes to the adsorption process. Styryl pyridinium dyes are found to anchor on silica surface in flat-on position. On modification of the silica by treating with alkali, the adsorption behaviour of cationic surfactant or polyethylene glycol changes due to change in the characteristics of silica or modified silica surface. In case of PEG-modified silica, adsolubilization of the adsorbate is observed. By using a modified adsorption equation, hemimicellization is proposed for these dyes. Adsorptions of some natural macromolecules like proteins and nucleic acids are investigated to study the hydrophobic and hydrophilic binding sites of silica. Artificial macromolecules like synthetic polymers are found to be adsorbed on silica surface due to the interaction of the multifunctional groups of the polymers with silanols. Preferential adsorption of polar adsorbates is observed in case of adsorbate mixtures. When surfactant mixtures are considered to study competitive adsorption on silica surface, critical micelle concentration of individual surfactant also contributes to the adsorption isotherm. The structural study of adsorbed surface and the thermodynamics of adsorption are given some importance in this review.     

Quantum theory of stimulated raman scattering in an inhomogeneously broadened three-level gaseous system

A quantum-statistical treatment of stimulated Raman scattering in a gaseous system is presented using a density-matrix formalism. The molecular (atomic) system is described by three energy levels. Both atomic system and the radiation fields are quantized. The effects of atomic motion and detuning are incorporated in the analysis. Higher order nonlinearities and loss terms are included to render the problem more realistic. The equations of motion describing the photonstatistics of pump and Stokes fields are obtained. The equation, without detailed balance, is solved in the steady-state by a slowly varying function technique in the case of two variables. The steady state characteristics of the Stokes field are studied. The coherence properties, occurrence of antibunching phenomena are studied for different initial distributions.     

"Click" synthesis and properties of carborane-appended large dendrimers

Large dendrimers, noted G(n)-3(n+2)cage, containing 3(n+2) o-carborane cluster cages MeC(2)B(10)H(10) at their peripheries (n = number of generation noted G(n)) have been synthesized by Huisgen-type azide alkyne Cu(I)-catalyzed dipolar "click" cycloaddition reactions (CuAAC) between an o-carborane monomeric cluster containing an ethynyl group and arene-centered azido-terminated dendrimers G(n)-3(n+2)N(3) of generations 0, 1, and 2. Attempts to synthesize higher-generation dendrimers of this family yielded insoluble materials. The carborane dendrimers G(0)-9cage, G(1)-27cage, and G(2)-81cage have been characterized by (1)H, (13)C, (11)B NMR, elemental analysis, matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectroscopy, and size exclusion chromatography (SEC) showing low polydispersities, dynamic light scattering (DLS) showing hydrodynamic diameters of 5.7 nm for the G(1)-27cage and the 12.9 nm for the G(2)-81cage. These dendrimers are extremely robust thermally, with 10% mass loss temperatures of 411 °C for the G(0)-9cage, 371 °C for the G(1)-27cage, and 392 °C for the G(2)-81cage. They all showed a strong absorption in the UV region peaking at 258 nm, whereas emission spectra of low intensities were observed between 280 and 480 nm.     

Comparative Pharmacokinetics Profile of Vasa Swaras with Vasicine and Vasicinone

An RP-LC method was developed and validated for comparing the pharmacokinetics profile of Vasa Swaras (leaf juice of Adhatoda vasica Nees., Fam. Acanthaceae) with that of the pure vasicine and vasicinone (chief marker compounds of A. vasica) upon oral administration of Vasa Swaras in rats, and also in different animal groups. Significant difference with p < 0.05 was found in the oral bioavailability of vasicine and vasicinone when administered as Vasa Swaras and as single vasicine and/or vasicinone. Vasicine and vasicinone were found to be more bioavailable from Vasa Swaras than pure vasicine and/or vasicinone.     

Proton radioactivity with a Yukawa effective interaction

The half-lives of proton radioactivity of proton emitters are investigated theoretically. Proton-nucleus interaction potentials are obtained by folding the densities of the daughter nuclei with a finite-range effective nucleon-nucleon interaction having Yukawa form. The Wood-Saxon density distributions for the nuclei used in calculating the nuclear as well as the Coulomb interaction potentials are predictions of the interaction. The quantum mechanical tunneling probability is calculated within the WKB framework. These calculations provide reasonable estimates for the observed proton radioactivity lifetimes. The effects of neutron-proton effective mass splitting in neutron-rich asymmetric matter as well as the nuclear matter incompressibility on the decay probability are investigated.     

The magnetization of PrFeAsO0.60F0.12 superconductor

The magnetization of the PrFeAsO_0.60F_0.12 polycrystalline sample has been measured as functions of temperature and magnetic field (H). The observed total magnetization is the sum of a superconducting irreversible magnetization and a paramagnetic magnetization. Analysis of dc susceptibility χ(T) in the normal state shows that the paramagnetic component of magnetization comes from the Pr³⁺ magnetic moments. The intragrain critical current density (J_L) derived from the magnetization data is large. The J_L(H) curve displays a second peak which shifts towards the high-field region with decreasing temperature. In the low-field region, a plateau up to a field H^* followed by a power law H^?5/8 behavior of J_L(H) is the characteristic of the strong pinning. A vortex phase diagram for the present superconductor has been obtained from the magnetization and resistivity data.     

Sample Treatment Approaches for Trace Level Determination of Cesium in Hepatitis B Vaccine by Suppressed Ion Chromatography

The hepatitis B surface antigen manufactured by recombinant DNA technology is extracted from the culture media by density gradient centrifugation using cesium salts. Cesium is considered to be toxic, because it affects active ion transport by blocking potassium channels. The residual trace levels of cesium in hepatitis B vaccine samples are determined by suppressed ion chromatography. Hepatitis B vaccines contain various buffer salts, aluminum-containing adjuvants, proteins and traces of iron. The polyvalent cations (Al³⁺, Fe³⁺) and proteins degrade the chromatographic performance in terms of decreased retention time and poor reproducibility. Different sample preparation approaches were evaluated with the aim of eliminating these foulants: (1) filtration, (2) digestion and (3) digestion-protein precipitation. Quantitative elimination of these foulants was achieved in the digestion-protein precipitation sample clean-up approach. Cesium was separated on the IonPac CS17 column with suppressed conductivity detection. The results of the ion chromatography (IC) method were compared with ICP-MS analysis. The precision of determination was better than 6.5% (relative standard deviation) with a method detection limit of 45 ng mL⁻¹. The expanded uncertainty in the measurement at 95% confidence level (coverage factor 2) is better than 16.3%.