Microwave extraction and rapid isolation of arjunic acid from Terminalia arjuna (Roxb. ex DC.) stem bark and quantification of arjunic acid and arjunolic acid using HPLC-PDA technique

Arjunic acid and arjunolic acid are main bioactive components of Terminalia arjuna stem bark and reported for various biological activities. In this study, microwave-assisted extraction (MAE) of arjunic and arjunolic acid from stem bark of T. arjuna was investigated with developed and validated HPLC-PDA method, which resulted in the isolation of a novel anticancer molecule i.e. arjunic acid. Effects of several experimental parameters, such as type and volume of extraction solvents, microwave power, microwave extraction time, on the extraction efficiencies of arjunic, and arjunolic acid from stem bark of T. arjuna were evaluated. The optimal extraction conditions identified were 5.0 g quantity of stem bark powder, 20 mL of ethyl acetate, preleaching time 10 min, microwave power 600 W, temperature 65°C, and microwave irradiation time 5 min. The results showed that MAE is a more rapid extraction method with higher yield and lower solvent consumptions than reported methods. The HPLC-PDA analysis method was developed and validated to have good linearity, precision, sensitivity, and accuracy. MAE-HPLC-PDA is a faster, convenient, and appropriate method for isolation and determination of arjunic acid and arjunolic acid in the stem bark of T. arjuna.     

Molecular precursors for the preparation of homogenous zirconia-silica materials by hydrolytic sol-gel process in organic media. Crystal structures of [Zr{OSi(O(t)Bu)3}4(H2O)2]·2H2O and [Ti(O(t)Bu){OSi(O(t)Bu)3}3

[Zr(OPr(i))(4)·Pr(i)OH] reacts with [HOSi(O(t)Bu)(3)] in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy zirconosiloxane precursors of the types [Zr(OPr(i))(3){OSi(O(t)Bu)(3)}] (A) and [Zr(OPr(i))(2){OSi(O(t)Bu)(3)}(2)] (B), respectively. Further reactions of A or B with glycols in 1:1 molar ratio afforded six chemically modified precursors of the types [Zr(OPr(i))(OGO){OSi(O(t)Bu)(3)}] (1A-3A) and [Zr(OGO){OSi(O(t)Bu)(3)}(2)] (1B-3B), respectively [where G = (-CH(2)-)(2) (1A, 1B); (-CH(2)-)(3) (2A, 2B) and (-CH(2)CH(2)CH(CH(3)-)} (3A, 3B)]. The precursors A and B are viscous liquids, which solidify on ageing whereas the other products are all solids, soluble in common organic solvents. These were characterized by elemental analyses, molecular weight measurements, FAB mass, FTIR, (1)H, (13)C and (29)Si-NMR studies. Cryoscopic molecular weight measurements of all the products, as well as the FAB mass studies of 3A and 3B, indicate their monomeric nature. However, FAB mass spectrum of the solidified B suggests that it exists in dimeric form. Single crystal structure analysis of [Zr{OSi(O(t)Bu)(3)}(4)(H(2)O)(2)]·2H(2)O (3b) (R(fac) = 11.9%) as well as that of corresponding better quality crystals of [Ti(O(t)Bu){OSi(O(t)Bu)(3)}(3)] (4) (R(fac) = 5.97%) indicate the presence of a M-O-Si bond. TG analyses of 3A, B, and 3B indicate the formation of zirconia-silica materials of the type ZrO(2)·SiO(2) from 3A and ZrO(2)·2SiO(2) from B or 3B at low decomposition temperatures (≤200 °C). The desired homogenous nano-sized zirconia-silica materials [ZrO(2)·nSiO(2)] have been obtained easily from the precursors A and B as well as from the glycol modified precursors 3A and 3B by hydrolytic sol-gel process in organic media without using any acid or base catalyst, and these were characterized by powder XRD patterns, SEM images, EDX analyses and IR spectroscopy.     

Preparation of a poly-nanocage dynamer: correlating the growth of polymer strands using constitutional dynamic chemistry and heteroleptic aggregation

A metallosupramolecular prismatic nanocage with altogether six reactive aldehyde terminals was utilized as a sophisticated "monomer" in a template-directed constitutional dynamic imine polymerization to prepare an unprecedented triple-stranded dynamer. To analyze the correlated growth in its three congener strands, a fully covalent triple-armed star polymer was fabricated from the metallodynamer through capping, imine reduction, and removal of the template. Atomic force microscopy analysis of 68 triple-armed star polymer molecules suggests that the growth of their arms is correlated to ~72%.     

Noncovalent surface grafting of uranium complexed cucurbit[5]uril oligomer onto palm shell powder: a novel approach for selective uranyl ion extraction

Biomass - that is a new feather in your cap: palm shell powder was used as support for novel uranyl complexed cucurbit[5]uril oligomer to obtain a selective extractant for uranium. The key to the selectivity lies in the perfect environment of the two portals of cucurbit[5]uril for uranyl ion binding.     

Enhanced light harvesting efficiencies of bis(ferrocenylmethyl)-based sulfur rich sensitizers used in dye sensitized TiO2 solar cells

In this work, the photosensitizing properties of ferrocene (Fc)-based compounds FcCH(2)CS(3)CH(2)Fc (1) and FcCH(2)SSCH(2)Fc (2) were investigated and significant enhancement in the light harvesting efficiency was observed compared to those achieved with previously reported compounds from our lab. The compounds were fully characterized by spectroscopy and X-ray crystallography, and their electrochemical properties studied. DSSCs based on these dyes display efficiencies comparable to those of a standard cell based on N719 under similar experimental conditions. These studies demonstrate that ferrocenyl-based sulfur rich compounds with proper orientation of the Fc groups assisted via suitable linkers, together with desired redox properties and visible region electronic absorption features could constitute a new class of photosensitizers targeting light driven reactions.     

First-order antiferro-ferromagnetic transition in Fe(49)(Rh(0.93)Pd(0.07))(51) under simultaneous application of magnetic field and external pressure

A magnetic field-pressure-temperature (H-P-T) phase diagram for first-order antiferromagnetic (AFM) to ferromagnetic (FM) transitions in Fe(49)(Rh(0.93)Pd(0.07))(51) has been constructed using resistivity measurements under simultaneous application of magnetic field (up to 8 T) and pressure (up to 20 kbar). The temperature dependence of resistivity (ρ-T) shows that the width of the transition and the extent of hysteresis decreases with pressure and increases with magnetic field. By exploiting opposing trends of dT(N)/dP and dT(N)/dH (where T(N) is the first-order transition temperature), the relative effects of temperature, magnetic field and pressure on disorder-broadened first-order transitions has been studied. For this, a set of H and P values are chosen for which T(N)(H(1),P(1)) = T(N)(H(2),P(2)). Measurements for such combinations of H and P show that the temperature dependence of resistivity is similar, i.e. the broadening (in temperature) of transition as well as the extent of hysteresis remains independent of H and P. Isothermal magnetoresistance measurements under various constant pressures show that even though the critical field required for AFM-FM transition depends on applied pressure, the extent of hysteresis as well as transition width (in magnetic field) remains constant with varying pressure.     

Metal exchange kinetics: uncatalyzed replacement of Ni(II) from tetramethylenediaminetetraacetatonickel(II) complex by Cu(II)

The kinetics of metal exchange between copper(II) and tetramethylenediaminetetraacetatonickel(II), [Ni(TMDTA)] has been studied between pH 3.4 and 4.8 at an ionic strength of 1.25 M (NaClO₄) and a temperature of 25.0 ± 0.1 °C. The reaction is first order in [Ni(TMDTA)]. The reaction order in [Cu²⁺] varies from first to zero and then back to first as [Cu²⁺] is increased. At low copper concentration, the first-order rate constant is pH independent and represents the attack of copper on the nickel complex through a pathway in which TMDTA is partially uncoordinated before reaction with copper. Evidence is presented for a stepwise dechelation mechanism followed by attack of copper to give a dinuclear intermediate. The zero-order rate is pH dependent. At higher [Cu²⁺], the swing back to first order is due to the formation of a weak copper-tetramethylenediaminetetraacetatonickelate complex which then converts to products through a dinuclear intermediate. A plausible mechanism, consistent with all the kinetic data, is presented.     

Simultaneous quantification of centchroman and its 7-demethylated metabolite in rat dried blood spot samples using LC-MS/MS

An approach has been developed for the quantitative determination of concentrations of centchroman ( I), a nonsteroidal once‐a‐week oral contraceptive, and its major metabolite (7‐desmethyl centchroman, II) using dried blood spots (DBS) on paper, rather than conventional plasma samples. The assay employed simple solvent extraction of the DBS sample circle (6 mm) requiring small blood volumes (30 μL) followed by reversed‐phase HPLC separation, combined with multiple reaction monitoring mass spectrometric detection. The calibration plot in matrix using d ‐trans‐hydroxy chroman as internal standard (IS) was linear (r² = 0.998) over ranges of 1.5–240 and 4.5–720 ng/mL for I and II, respectively. The recoveries of both I and II were always >60% with quantification limits (signal‐to‐noise ratio = 10) of 1.5 and 4.5 ng/mL for I and II, respectively. The intra‐day and inter‐day precision (%RSD) and accuracy (%bias) variations in blood spots for both I and II were better than 13%. Moreover, both I and II were stable in DBS for at least 3 months when stored at room temperature. The developed method was successfully applied to the pharmacokinetic interaction study after oral administration of centchroman with and without co‐administration of carbamazepine in female Sprague–Dawley rats using serial sampling and results were comparable with the plasma concentrations reported earlier. Copyright © 2011 John Wiley & Sons, Ltd.     

Passively Q-switched diode-pumped Raman laser with third-order Stokes eye-safe oscillation

We demonstrate a passively Q-switched all-solid-state laser system with intracavity Raman frequency conversion to the eye-safe spectral region. Laser oscillation at the 1.064 μm wavelength with a pulse repetition rate of several kilohertz was provided by a Nd:YAG crystal and a Cr:YAG passive absorber. Third Stokes oscillations at the 1.599 and 1.494 μm wavelengths were obtained in Ba(NO₃)₂ and PbWO₄ crystals with output pulse energies of 5 μJ and 6 μJ, respectively. The results of the numerical simulation of the pulse dynamics are in good agreement with the experimental data.     

NHC-catalysed diastereoselective synthesis of multifunctionalised piperidines via cascade reaction of enals with azalactones

NHC-catalysed azalactone ring-opening and piperidine ring-closing cascade with α,β-unsaturated aldehydes (enals) in a one-pot operation is reported. The present reaction cascade offers a convenient method for a highly diastereoselective synthesis of multifunctionalised piperidines in excellent yields under mild conditions.