Application of high performance liquid chromatography coupled to on-line solid-phase extraction-nuclear magnetic resonance spectroscopy for the analysis of degradation products of V-class nerve agents and nitrogen mustard

The detection and identification of the degradation products of nitrogen mustard and nerve agent VX by high performance liquid chromatography coupled to on-line solid-phase extraction-nuclear magnetic resonance spectroscopy (HPLC-UV-SPE-NMR) were demonstrated. The analytes selected for the study were N,N-dimethylaminoethanol (DMAE), N,N-diethylaminoethanol (DEAE), N,N-diisopropylaminoethanol (DIAE) and triethanolamine (TEA). Offline solid-phase extraction (SPE) followed by derivatization was applied to eliminate the interferents and make the analytes amenable for UV detection. Thereafter, chromatographically separated derivatives were trapped on on-line SPE cartridges. They were subsequently eluted and ¹H NMR and COSY spectra were obtained. The overall detection limits of the LC-UV-SPE-NMR method for the mentioned analytes were found to be 18, 23, 25, and 32 mg/L respectively. Applicability of the method to real samples was demonstrated by the analysis of samples provided during the 22nd OPCW official proficiency test. The method gave reproducible NMR spectra devoid of intense background signals.     

Higher order B-spline differential quadrature rule to approximate generalized Rosenau-RLW equation

In this article, B-spline-based collocation method is employed to approximate the usual and modified Rosenau-RLW nonlinear equations. The weighted extended B-spline (WEB-spline) is used as the modified form of B-spline as the usual B-splines fail to obey the Dirichlet boundary conditions. The WEB method is more general method that allows to discretize the domain into finite number of elements not necessarily start from the boundary points of the domain. Our method omits the linearization process of the nonlinear partial differential equation (PDE). Different cases are discussed by setting the parameter p=2,3,4, and 6 that appears in Rosenau-RLW equations. The error estimation is calculated, which gives good agreement of the exact solution.     

Development and Validation of HPTLC Densitometric Method for Identification and Quantification of Geraniol in Palmarosa Oil

JPC – Journal of Planar Chromatography – Modern TLC - India is the main producer of palmarosa oil obtained from rosha grass (Cymbopogan martini var. motia) of family Graminae. The...     

Simultaneous estimation of 16α-hydroxycleroda-3,13(14) Z-dien-15,16-olide from Polyalthia longifolia and its metabolite in hamster plasma: application to pharmacokinetic study

A selective and sensitive LC–MS‐MS method was developed and validated for simultaneous estimation and pharmacokinetic studies of 16α‐hydroxycleroda‐3,13(14) Z‐dien‐15,16‐olide (K‐09) obtained from Polyalthia longifolia and its metabolite (K‐9T), a novel antidyslipidemic agent. Sample clean‐up involved liquid–liquid extraction of both the analytes and internal standard (rosuvastatin) from 200 μL of hamster plasma. The analytes were chromatographically separated on a Symmetry‐Shield C₁₈ (5 µm, 4.6 × 150 mm) column, using acetonitrile–0.1% aqueous formic acid (92:08, v/v) as the mobile phase. Detection was performed using negative ion electrospray ionization in multiple reaction monitoring mode. The MS/MS response was linear over the concentration range 1.56–200 ng/mL, with a correlation coefficient (r²) of 0.998 or better. The within‐ and between‐batch precisions (relative standard deviation, %RSD) and the accuracy (percentage bias) were within acceptable limits as per FDA guidelines. The validated method was successfully applied to reveal the pharmacokinetic parameters of K‐09 and metabolite after oral administration. This method will therefore be highly useful for future studies of K‐09 and metabolite K‐9T pharmacokinetics in preclinical and clinical studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Capacitively coupled contactless conductivity detection with dual top–bottom cell configuration for microchip electrophoresis

An optimized capacitively coupled contactless conductivity detector for microchip electophoresis is presented. The detector consists of a pair of top–bottom excitation electrodes and a pair of pickup electrodes disposed onto a very thin plastic microfluidic chip. The detection cell formed by the electrodes is completely encased and shielded in a metal housing. These approaches allow for the enhancement of signal coupling and extraction from the detection cell that result in an improved signal‐to‐noise‐ratio and detection sensitivity. The improved detector performance is illustrated by the electrophoretic separation of six cations (NH, K⁺, Ca²⁺, Na⁺, Mg²⁺, Li⁺) with a detection limit of approximately 0.3 μM and the analysis of the anions (Br^?, Cl^?, NO, NO, SO, F^?) with a detection limit of about 0.15 μM. These LODs are significantly improved compared with previous reports using the conventional top–top electrode geometry. The developed system was applied to the analysis of ions in bottled drinking water samples.     

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method for the non-phosphorus markers of chemical warfare agents

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method has been developed for detection, identification and quantification of non-phosphorus markers of toxic nerve agents (soman and V-class), vesicants (HD, HN-2, HN-3), and incapacitating agent (Bz). These analytes were converted to phosphorus-containing derivatives via phosphitylation reaction of their hydroxyl and sulfhydryl functions (using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane). This was followed by ³¹P{¹H} and ³¹P NMR analysis of these derivatives. The chemical shifts (δ) and coupling constants (³ J _P–H) of derivatives were used for their specific detection and identification. The method allowed clear distinction between the alcohols and thiols. The lower limits of detection of these analytes were found to be between 12 and 28 μg obtained from 128 transients of ³¹P{¹H} quantitative NMR experiments. Utility of the method was ensured by the detection and identification of triethanolamine present (at an original concentration of 5 μg/mL) in an aqueous sample from 28th OPCW Official Proficiency Tests.     

Computational study on the conformational preferences in nateglinide

Ab initio and semi‐empirical calculations were performed on the monomers, dimers and tetramers of the antidiabetic drug nateglinide to understand the conformational preferences and to explore their possible relation with polymorphism. The reported crystal structure of bis(nateglinide) hydronium chloride shows one asymmetric unit consisting of four different conformations of the drug nateglinide. The Becke, three‐parameter, Lee–Yang–Parr /6‐31+G(d,p) optimizations indicate that these conformers are energetically quite comparable and the differences disappear in gas phase. Our analysis shows that Φ (phi) torsion angle of this phenylalanine derivative is responsible for the observed differences in stability among the nateglinide conformations. Four different polymorphs of nateglinide (B, H, S and X2) were reported but the structural differences are not available. This quantum chemical study on the dimers of nateglinide helps in proposing the structures of polymorphs. As per the quantum chemical analysis, the dimer N‐44 is the structure of the stable polymorph, whereas, the dimers N‐AA, N‐CC and N‐AC are almost isoenergetic, thus proposed to be the structures of metastable state. The dimerization and tetramerization energies are estimated to be about ?9.0 and ?38.67 kcal/mol, respectively. The extra stability in tetrameric state compared with the dimeric form is attributed to additional hydrophobic and van der Waals interactions. Copyright © 2011 John Wiley & Sons, Ltd.     

Gas chromatography/mass spectrometric analysis of N,N-dialkylaminoethyl-2-chlorides and trimethylsilyl derivatives of N,N-dialkylaminoethan-2-ols for verification of the Chemical Weapons Convention

Gas chromatography/electron ionization mass spectrometry (GC/EI-MS) of N,N-dialkylaminoethyl-2-chlorides (DAAECls) and trimethylsilyl (TMS) derivatives of N,N-dialkylaminoethan-2-ols (DAAEAs) has been carried out. GC/EI-MS data of these compounds are of importance for verification of the Chemical Weapons Convention (CWC). Based on these EI mass spectra, generalized fragmentation routes are proposed that rationalize most of the characteristic ions.     

Study of higher order non-classical properties of squeezed Kerr state

Recently, Prakash and Mishra [J. Phys. B: at. Mol. Opt. Phys., 39, 2291(2006); 40, 2531(2007)] have studied higher order sub-Poissonian photon statistic conditions for non-classicality in the form of general inequalities for expectation values of products of arbitrary powers of photon number and of photon-number fluctuation. It is, therefore, vital to study the generation of these higher order sub-Poissonian photon statistics (phase-insensitive behavior) in a physically realizable medium and their relations to higher order squeezing (phase-sensitive behavior). In the present paper, we study higher order non-classical properties, such as Hong and Mandel squeezing, amplitude-squared squeezing and higher order sub-Poissonian photon statistics, of squeezed Kerr state which is generated by squeezing the output of a Kerr medium whose input is coherent light. Such states can be realized if laser light is sent through an optical fiber and then into a degenerate parametric amplifier. It is established that the squeezed Kerr state can exhibit higher order non-classical properties.     

Synthesis and Characterization of Phthalonitrile-Capped Phthalimido Anhydrides

The condensation in an aprotic solvent of 4-aminophthalonitrile with hexafluoroisopropylidenediphthalic anhydride (6FA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BPTDA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), and bisester anhydride (BEA), respectively, gave the corresponding phthalamic acids. These phthalmic acids were thermally cyclodehydrated to give phthalonitrile-capped phthalimido anhydrides. Elemental analysis, differential thermal analysis (DSC), Fourier-transform infrared (FTIR), and nuclear magnetic resonance (¹H NMR) studies were used to characterize these anhydrides. The mass spectra of these compounds suggest a mechanism for their fragmentation.