Probing of Metabolites in Finely Powdered Plant Material by Direct Laser Desorption Ionization Mass Spectrometry

Natural products continue to serve as an important source of novel drugs since the beginning of human history. High-throughput techniques, such as MALDI-MS, can be techniques of choice for the rapid screening of natural products in plant materials. We present here a fast and reproducible matrix-free approach for the direct detection of UV active metabolites in plant materials without any prior sample preparation. The plant material is mechanically ground to a fine powder and then sieved through different mesh sizes. The collected plant material is dispersed using 1 μL solvent on a target plate is directly exposed to Nd:YAG 335 nm laser. The strategy was optimized for the analysis of plant metabolites after study of the different factors affecting the reproducibility and effectiveness of the analysis, including particle sizes effects, types of solvents used to disperse the sample, and the part of the plant analyzed. Moreover, several plant species, known for different classes of metabolites, were screened to establish the generality of the approach. The developed approach was validated by the characterization of withaferin A and nicotine in the leaves of Withania somnifera and Nicotiana tabacum, respectively, through comparison of its MS/MS data with the standard compound. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques were used for the tissue imaging purposes. This approach can be used to directly probe small molecules in plant materials as well as in herbal and pharmaceutical formulations for fingerprinting development.      

CHLOROSULFONATION OF 9-ARYLOCTAHYDROXANTHEN-1,8-DIONES

The 9-aryloctahydroxanthen-1,8-diones (3, 4– 24) were prepared by reaction of cyclohexan-1,3-dione (1) with selected arylaldehydes. The xanthendiones (4– 9, 11, 12, 18, 21, 22) were successfully reacted with chlorosulfonic acid, and the crude sulfonyl chlorides were converted into 15 sulfonamides (26– 40) for screening as potential pesticides. Attempted chlorosulfonation of the xanthendiones (13– 17) was unsuccessful. α-Methylcinnamaldehyde was reacted with cyclohexandione (1) to yield the corresponding xanthendione derivative (23). On the other hand, with o-methoxycinnamaldehyde an impure product formed and the p-methoxy isomer afforded the corresponding 2-arylpyran (25). The NMR spectral data of the compounds are briefly discussed.     

Arsenic speciation and other parameters of surface and ground water samples of Jamshoro,Pakistan

This study evaluated and interpreted complex data sets of water samples collected from different sampling origins of ground water (hand pump and tube well) and surface water (municipal, river and canal). The aim was to provide information concerning the apportionment of pollution sources to obtain better information about water quality and possible distribution of As with respect to its speciation. The As (III) formed complex with ammonium pyrrolidinedithiocarbamate (APDC) and extracted by surfactant-rich phases in the non-ionic surfactant Triton X-114, while total iAs in water samples was adsorbed on titanium dioxide (TiO₂) and determined by electrothermal atomic absorption spectrometry. The accuracy of the proposed methodologies was confirmed by standard addition method. The recoveries of As (III) and total inorganic arsenic (iAs) were found to be >98%. The results revealed that the ground water of the area under study was more contaminated as compared to surface water samples. The mean concentration of As (III) and As (V) in the surface water samples was found to be 15.8 and 6.00?µg?L^?1, respectively, whereas, in the case of ground water samples, the contents of As (III) and As (V) ranged from 6.20 to 51.0 and 6.40 to 53.0?µg?L^?1, respectively. Principal component analysis performed on a combined (tube well and hand pump) samples data set extracted two significant factors explaining more than 60% of total variance, which suggested that the contamination sources might be natural or anthropogenic.     

Numerical spectral examination of EMHD mixed convective flow of second-grade nanofluid towards a vertical Riga plate using an advanced version of the revised Buongiorno’s nanofluid model

Journal of Thermal Analysis and Calorimetry - Present communication aims to determine the impact of Cattaneo–Christov model and convective boundary on second-grade nanofluid flow alongside a...     

Structural, elastic constant, and vibrational properties of wurtzite gallium nitride: a first-principles approach

Perdew-Wang proposed generalized gradient approximation (GGA) is used in conjunction with ultrasoft pseudopotential to investigate the structural, elastic constant, and vibrational properties of wurtzite GaN. The equilibrium lattice parameters, axial ratio, internal parameter, bulk modulus, and its pressure derivative are calculated. The effect of pressure on equilibrium lattice parameters, axial ratio, internal parameter (u), relative volume, and bond lengths parallel and perpendicular to the c-axis are discussed. At 52 GPa, the relative volume change is observed to be 17.8%, with an abrupt change in bond length. The calculated elastic constants are used to calculate the shear wave speeds in the [100] and [001] planes. The finite displacement method is employed to calculate phonon frequencies and the phonon density of states. The first- and second-order pressure derivative and volume dependent Gruneisen parameter (γ(j)) of zone-center phonon frequencies are discussed. These phonon calculations calculated at theoretical lattice constants agree well with existing literature.     

Valuation of Two-Factor Interest Rate Contingent Claims Using Green's Theorem

Abstract

Over the years a number of two-factor interest rate models have been proposed that have formed the basis for the valuation of interest rate contingent claims. This valuation equation often takes the form of a partial differential equation that is solved using the finite difference approach. In the case of two-factor models this has resulted in solving two second-order partial derivatives leading to boundary errors, as well as numerous first-order derivatives. In this article we demonstrate that using Green's theorem, second-order derivatives can be reduced to first-order derivatives that can be easily discretized; consequently, two-factor partial differential equations are easier to discretize than one-factor partial differential equations. We illustrate our approach by applying it to value contingent claims based on the two-factor CIR model. We provide numerical examples that illustrate that our approach shows excellent agreement with analytical prices and the popular Crank–Nicolson method.     

A note on teleparallel Killing vector fields in Bianchi type VIII and IX spaceben times in teleparallel theory of gravitation

In this paper we classify Bianchi type VIII and IX space—times according to their teleparallel Killing vector fields in the teleparallel theory of gravitation by using a direct integration technique. It turns out that the dimensions of the teleparallel Killing vector fields are either 4 or 5. From the above study we have shown that the Killing vector fields for Bianchi type VIII and IX space—times in the context of teleparallel theory are different from that in general relativity.     

Fukuyama reduction,Fukuyama coupling and Fukuyama–Mitsunobu alkylation: recent developments and synthetic applications

Fukuyama reaction for the synthesis of multifunctional aldehydes, secondary amines and ketones has gained considerable importance in synthetic organic chemistry because of mild reaction conditions. The use of thioesters in both Fukuyama aldehydes and ketones synthesis is highly attractive for organic chemists as they are easily accessible from corresponding carboxylic acids. Fukuyama–Mitsunobu reaction utilizes 2-nitrobenzenesulfonyl (Ns) for the protection/activation/deprotection of primary amines to afford secondary amines in good yields and high enantioselectivities. This review presents recent synthetic developments and applications of Fukuyama reaction for the synthesis of aldehydes, secondary amines and ketones.

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