Direct and simultaneous profiling of epoxyeicosatrienoic acid enantiomers by capillary tandem column chiral-phase liquid chromatography with dual online photodiode array and tandem mass spectrometric detection

Despite first evidence for the cytochrome P450-mediated enantioselective biosynthesis and activity of cis-epoxyeicosatrienoic acids (EETs), as yet little is known about the stereospecifity of EET generation and physiology, because the existing chiral methods are time consuming, labor intensive, and not sensitive enough. We present a method for highly sensitive, direct, and simultaneous chiral analysis of all eight EET enantiomers consisting of (i) solid-phase extraction, (ii) reversed-phase high-performance liquid chromatographic purification followed by (iii) consecutive regio- and enantiomeric separation of the four underivatized EET regioisomers within one chromatographic run employing capillary tandem column chiral-phase liquid chromatography with (iv) reliable dual online photodiode array and gentle electrospray ionization tandem mass spectrometric identification and quantitation of the eluting optical antipodes. This one-step, simple, expeditious, and highly sensitive measurement allows profiling of all eight EET enantiomers at once, thus avoiding substance loss and enabling high sample throughput. Limits of quantification in the low picogram range were achieved by the use of capillary columns with typical high quantitative sensitivity instead of conventional columns with low chromatographic signal intensity employed by previous methods. Application to tissue homogenates demonstrated the suitability of this approach for routine and reliable “enantioprofiling” of free endogenous EETs, i.e., EETs not esterified into cellular membrane phospholipids, typically occurring at very low concentrations. The technique can readily be employed for preparative purification of enantiomers in the microgram range using large-inner-diameter columns. Figure Direct and simultaneous enantioprofiling of the four free endogenous epoxyeicosatrienoic acids (EETs) from a complex biological matrix, like the cardiopulmonary system, within one chromatographic run by highly sensitive, one-step capillary tandem column chiral-phase liquid chromatography with dual online photodiode array and tandem mass spectrometric detection (CapTC-CP-LC-PDAD-ESI-MS²) enables accurate, systematic, and routine correlation between the absolute configuration of EETs and their physiological actions Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Development of some important nitrogen donor ligands for transition metal homogeneous catalysis

This review provides a broad overview of the literature related to the importance of ligands in homogeneous catalysis. In particular, it describes the types of nitrogen donor ligands that have typically been used for homogeneous catalysis. We surveyed the important transition metal homogenous catalysts explicitly from 2011 up to early 2014 and summarize their comparative catalytic activities. Generally, the main factors observed are the ligand structure, electron donor property and steric bulk which can affect the catalytic activity. Electron count and inductive effect can also influence the efficiency of homogeneous catalyst.     

Generalized Bessel Functions and Lie Algebra Representation

The generalized Bessel functions (GBF) are framed within the context of the representation Q(ω,m ₀) of the three-dimensional Lie algebra . The analysis has been carried out by generalizing the formalism relevant to Bessel functions. New generating relations and identities involving various forms of GBF are obtained. Certain known results are also mentioned as special cases.Mathematics Subject Classifications (2000) 33C10, 33C80, 33E20.     

Determination of Phase Space Spectra of the Generalized Chiral Schwinger model with the Lorentz invariant Mass like Term for the Choice a − r2 = 0

We have considered the generalized version of chiral schwinger model with the Lorentz covariant masslike term for gauge field with the choice a ? r² =?0. We carry out the quantization by the canonical Dirac method of both the gauge-invariant and non-invariant version of this model to determine the phase space structure. Therefore we have shown that the gauge invariant theory has the same physical spectrum as that of the original gauge noninvariant formulation.

     

Convective and peristaltic viscous fluid flow with variable viscosity

In the present investigation we have analyzed the peristaltic flow when the viscous fluid with variable viscosity is bounded with convective walls. The combined effects of thermaldiffusion (Soret effects) and diffusion-thermo (Dufour effect) are considered. Convective form of the heat and mass transport phenomenon has been given special attention in addition to the effects of magnetic field. Mathematical formulation for the physical systemis derived and simplified using long wavelength and low Reynolds number approximation. Series solutions for the velocity, temperature andmass concentration fields are computed and elaborated for different physical quantities including magnetic parameter, Soret and Dufour effects, Biot numbers, etc. Streamlines analysis is presented showing the effects of bolus movement.     

Generalized and mixed type Gegenbauer polynomials

In this paper, a new generalized form of the Gegenbauer polynomials is introduced by using the integral representation method. Further, the Hermite–Gegenbauer and the Laguerre–Gegenbauer polynomials are introduced by using the operational identities associated with the generalized Hermite and Laguerre polynomials of two variables.