Sorption study of U(VI), Th(IV) and Ce(III) on poly[dibenzo-18-crown-6] in <Emphasis Type="SmallCaps">l</Emphasis>-arginine to develop sequential column chromatographic separation method

A simple and efficient column chromatographic method has been developed for the sequential separation of U(VI), Th(IV) and Ce(III) using poly[dibenzo-18-crown-6] as stationary phase and l-arginine as a counter ion. The different elution patterns with various eluting agents were observed for individual element. The capacity of poly[dibenzo-18-crown-6] for U(VI), Th(IV) and for Ce(III) was found to be 0.96, 0.86 and 1.49 (±0.01) mmol/g of crown polymer, respectively. The method is efficient to separate the elements in multicomponent mixtures and has good recovery. The method is extended to determine the U(VI), Th(IV) and Ce(III) from monazite sand. The method is simple, rapid and selective having good reproducibility (~±2%).     

Metal catalyst-free direct α-iodination of ketones with molecular iodine

Ketones are directly converted to the corresponding α-iodoketones in good yields with molecular iodine under metal catalyst-free conditions. A significant difference in the reactivities was observed for aliphatic and aromatic ketones; whereas aliphatic ketones reacted smoothly at room temperature giving a mixture of 1-iodo, 3-iodo and 1,3-diiodoketones with predominant formation of the 3-iodo product, the α-iodination of aromatic ketones proceeded conveniently under heating to give good yields of α-iodo products.     

Structure Elucidation and Activity of Kolossin A,the D‐/L‐Pentadecapeptide Product of a Giant Nonribosomal Peptide Synthetase

The largest continuous bacterial nonribosomal peptide synthetase discovered so far is described. It consists of 15 consecutive modules arising from an uninterrupted, fully functional gene in the entomopathogenic bacterium Photorhabdus luminescens. The identification of its cryptic biosynthesis product was achieved by using a combination of genome analysis, promoter exchange, isotopic labeling experiments, and total synthesis of a focused collection of peptide candidates. Although it belongs to the growing class of D ‐/ L ‐peptide natural products, the encoded metabolite kolossin A was found to be largely devoid of antibiotic activity and is likely involved in interspecies communication. A stereoisomer of this peculiar natural product displayed high activity against Trypanosoma brucei rhodesiense, a recalcitrant parasite that causes the deadly disease African sleeping sickness.     

Calotropis procera extract induces apoptosis and cell cycle arrest at G2/M phase in human skin melanoma (SK-MEL-2) cells

Calotropis procera (family: Asclepiadaceae) contains cardiac glycosides which are cytotoxic to cancer cells. The extracts of C. procera have been reported to be cytotoxic to many cancer cell lines and this is the first report against the human skin melanoma cells (SK-MEL-2). The SK-MEL-2 cells treated with C. procera methanolic extract (CPME) were analysed for growth inhibition and apoptosis. The exposure of phosphatidylserine in apoptotic SK-MEL-2 was analysed by using the Annexin-V FITC flow cytometry method. In CPME-treated SK-MEL-2 cells, 19.6% of apoptotic and 58.3% dead cells were observed. The 15.97% and 15.85% of early apoptotic cells were found at 20 μg/mL of the ouabain and paclitaxel, respectively. Active caspases, nuclear degradation confirmed apoptotic SK-MEL-2 cells in time- and dose-dependent manner. The cell cycle analysis shows that CPME treated cells halt at G2/M phase. Significant cytotoxic activity of CPME against SK-MEL-2 may be attributed to its high cardenolide content.     

NiO@CuO@Cu bilayered electrode: two-step electrochemical synthesis supercapacitor properties

Present work deals with a two-step synthesis and electrochemical properties of nickel oxide @copper oxide@copper (NiO@CuO@Cu) bilayered electrode. In the first step, anodization (40 V for 25 min) of Cu foil has been carried out for forming Cu-hydroxide@Cu which when annealed at 300 °C for 1 h produces CuO@Cu. In the second step, Ni-hydroxide is deposited onto CuO@Cu by applying current density of 0.03 A/cm² for 3 min which when re-annealed at 300 °C for 1 h gives out NiO@CuO@Cu bilayered electrode. Obtained NiO@CuO@Cu bilayered electrode demonstrates separate CuO and NiO phases. The electrochemical properties have obtained using cyclic voltammetry, galvonostatic charge-discharge, and Nyquist plot measurements that reveal an importance of NiO@CuO@Cu as a potential electrode material in the electrochemical supercapacitor application with 58.14, 51.25, and 4.73 F g^?1 values in 0.5 M, NaOH, KOH, and Na₂SO₄ electrolytes, respectively, measured at 2 mVs^?1 scan rate.     

Computational studies on tetrazole derivatives as potential high energy materials

The tetrazole is an important functionality of the most of energetic materials due to 80% nitrogen content, stability, and high enthalpy of formation. The present structure–property relationship study focuses on the optimized geometries of tetrazole derivatives obtained from density functional theory (DFT) calculations at B3LYP/6-31G* levels. The heat of formation (HOF) of tetrazole derivatives have been calculated by designing the appropriate isodesmic reactions. The increase in nitro groups on azole rings shows the remarkable increase in HOF. Density has been predicted by using CVFF force field. Increase in the nitro group increases the density. Detonation properties of the designed compounds were evaluated by using the Kamlet–Jacobs equation based on predicted densities and HOFs. Designed tetrazole derivatives show detonation velocity (D) over 8 km/s and detonation pressure (P) of about 32 GPa. Thermal stability was evaluated via bond dissociation energies (BDE) of the weakest C–NO₂ bond at B3LYP/6-31G* level. Charge on the nitro group has been used to assess the sensitivity correlation. Overall, the study implies that designed compounds of this series are found to be stable and expected to be the novel candidates of high energy materials (HEMs).     

Multiresidue analysis of multiclass plant growth regulators in grapes by liquid chromatography/tandem mass spectrometry

A selective and rapid multiresidue analysis method is presented for simultaneous estimation of 12 plant growth regulators (PGRs), namely, auxins (indol-3-acetic acid, indol-3-butyric acid, and naphthyl acetic acid), cytokinins (kinetin, zeatin, and 6-benzyladenine), gibberellic acid (GA3), abscisic acid, and synthetic compounds, namely, forchlorfenuron, paclobutrazole, isoprothiolane, and 2,4-dichlorophenoxy acetic acid (2,4-D) in bud sprouts and grape berries at the development stages of 2-3 and 6-8 mm diameters, which are the critical phases when exogenous application of PGRs may be necessary to achieve desired grape quality and yield. The sample preparation method involved extraction of plant material with acidified methanol (50%) by homogenization for 2 min at 15000 rpm. The pH of the extract was enhanced up to 6 by adding ammonium acetate, followed by homogenization and centrifugation. The supernatant extract was cleaned by SPE on an Oasis HLB cartridge (200 mg, 6 cc). The final extract was measured directly by LC/MS/MS with electrospray ionization in positive mode, except for 2,4-D, GA3, and abscisic acid extracts, which required analysis in negative mode. Quantification by multiple reaction monitoring (MRM) was supported with full-scan mass spectrometric confirmation using "information-dependent acquisition" triggered with MRM to "enhanced product ionization" mode of the hybrid quadrupole-ion trap mass analyzer. The LOQ of the test analytes varied between 1 and 10 ng/g with associated recoveries of 80-120% and precision RSD <25% (n = 8). Significant matrix-induced signal suppression was recorded when the responses for pre- and postextraction spikes of analytes were compared; this could be resolved by using matrix-matched calibration standards. The method could successfully be applied in analyzing incurred residue samples and would, therefore, be useful in precisely deciding the necessity and dose of exogenous applications of PGRs on the basis of measured endogenous levels.     

A Stress Stability Behavior and Development of an LC Assay Method for Anastrozole

This present work narrates the stress stability behavior and development of a liquid chromatographic method for the quantitative determination of anastrozole. Anastrozole is appropriately used when using substantial amounts of aromatizing steroids, or when one is prone to gynecomastia and using moderate amounts of such steroids. A chromatographic separation was achieved on a Hichrom RPB18 (250 × 4.6 mm, 5 μ) column using water and mixture of acetonitrile and methanol (1:1 ratio) as mobile phase. Forced degradation studies were performed on bulk samples of anastrozole using acid, base, hydrogen peroxide, heat and UV light. Degradation of the drug substance was observed in base hydrolysis. Degradation product formed under base hydrolysis was found to be Imp-C. The sample solution and mobile phase were found to be stable up to 48 h. The developed method was validated with respect to linearity, accuracy, precision, robustness and forced degradation studies prove the stability indicating power of the method.     

A Validated Stability-Indicating LC Method for Zonisamide

A simple, isocratic, rapid, and accurate reversed-phase high-performance liquid chromatographic method has been established for quantitative determination of zonisamide. The method is also applicable to determination of related substances in the bulk drug. Chromatographic separation was achieved on a 250 mm × 4.6 mm, 5-μm particle, C₁₈ column; the mobile phase was a 70:30 (v/v) mixture of 0.1% (v/v) aqueous triethylamine, adjusted to pH 2.5 with dilute orthophosphoric acid, and acetonitrile. Chromatographic resolution of zonisamide from its potential impurity, A, was found to be >2. The limits of detection and quantification of zonisamide and impurity A were 0.04 and 0.12 μg mL⁻¹, respectively, for 20 μL injection volume. Recovery of zonisamide ranged from 98.5 to 101.2% and recovery of impurity A from a sample of zonisamide ranged from 97.4 to 102.7%. The method was validated for linearity, accuracy, precision, and robustness.

     

Kinetics and mechanism of oxidation of dimethyl sulfoxide by chloramine-T in aqueous solution

The kinetics of oxidation of dimethyl sulfoxide (DMSO) by chloramine-T (CAT) is studied in HClO₄ and NaOH media with OsO₄ as a catalyst in the latter medium. In acid medium, the rate law is -d [CAT]/dt = k [CAT][DMSO][H⁺]. Alkali retards the reaction and the rate law takes the form -d [CAT]/dt = k [CAT][DMSO][OsO₄]/[NaOH], but is reduced to -d [CAT]/dt = k [CAT][DMSO] at higher alkali concentrations. The reaction is subjected to changes in (a) ionic strength, (b) concentrations of added neutral salts, (c) concentrations of added reaction product, (d) dielectric constant, and (e) solvent isotope effect, and the subsequent effects on the reaction rate are studied. The reaction mechanism in acid medium assumes an electrophilic attack by the free acid RNHCl (CAT′) at the sulfur site in DMSO, forming a reaction intermediate which subsequently decomposes to dimethyl sulfone on hydrolysis. Formation of a cyclic complex between RNHCl and OsO₄ which interacts with the substrate in a slow step explains the observed results in alkaline medium. The simplification of the rate equation at higher alkali concentrations is attributed to a direct reaction between chloramine-T and the substrate.