Chemical synthesis of deuterium-labeled and unlabeled very long chain polyunsaturated fatty acids

First syntheses of a deuterium-labeled very long C34-containing polyunsaturated fatty acid, 34:5n5, and three other unlabeled very long chain C30-32 containing polyunsaturated fatty acids are reported. These syntheses were achieved by coupling chemically modified C22- and C20-containing polyunsaturated fatty acids with carbanions derived from arylalkyl sulfones, followed by sodium amalgam-mediated desulfonylation.     

Synthesis,Characterization and Fluorescence Studies of Novel Tetrachloroperylene-Azo Hybrid Dyes

Novel rylene-azo hybrid dyes have been synthesized by condensation of azo-dyes with tetrachloroperylene dianhydride, possessing stupendous thermal, chemical and photochemical stability. Phenolic azo dyes are used for the nucleophilic replacement of chlorine substituents at 1,6,7,12-positions of perylene 3,4,9,10-dianhydride system. The absorption maxima (?_max) of these dyes have been determined in diverse solvents such as water, ethanol, methanol, ethyl acetate and N, N-dimethylformamide. Fluorescence spectra are taken in water and highest fluorescence was exhibited by dyes containing carboxylic groups. The ?_max and fluorescence of these dyes is greatly affected by polarity of solvents. The structures of newly synthesized rylene-azo hybrid dyes have been confirmed by UV, FTIR and ¹HNMR spectroscopy.     

Zinc and iron determination in serum and urine samples of thyroid patients using cloud point extraction

A simple and rapid cloud point extraction method was applied for preconcentration of trace quantities of zinc (Zn) and iron (Fe) in biological samples (serum and urine) of thyroid patients prior to determination by flame atomic absorption spectrometry. The metals in serum and urine samples were complexed with 1-(2-thiazolylazo)-2-naphthol and entrapped in the surfactant octylphenoxypolyethoxyethanol (Triton X-114). After centrifugation, the surfactant-rich phase was diluted with 0.1 M HNO3 in methanol. For optimum recovery of analytes, the influences of the analytical parameters, including pH and amounts of complexing and surfactant reagents, were investigated. Enrichment factors of 66.4 and 70.2 were obtained for the preconcentration of Zn(II) and Fe(III), respectively. The obtained results showed sufficient recoveries (>98%) for Zn(II) and Fe(III) in certified reference materials (CRMs). The proposed method was applied to the determination of Zn(II) and Fe(III) in biological (serum and urine) samples and CRMs.     

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.      

Effect of Cosolvent on Bulk and Interfacial Characteristics of Imidazolium Based Room Temperature Ionic Liquids

Here we report a systematic study on electrical conductivity and surface tension of various concentrated solutions of imidazolium based room temperature ionic liquids (RTILs), viz. 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][ $\hbox {PF}_{6}$ ]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][ $\hbox {BF}_{4}$ ]) in the cosolvents methanol and acetonitrile at 298.15 K. The aim of the investigations was to explore the impact of cosolvents on bulk and interfacial characteristics of imidazolium based RTILs. It was observed that both methanol and acetonitrile mix non-ideally with and enhance the transport parameters of the imidazolium based RTILs. An interesting outcome of the presented work is that the investigated RTILs retain their inherent structural characteristics up to a high dilution limit with cosolvent, and this limit is higher in acetonitrile than in methanol as cosolvent. The findings establish that, in comparison to methanol, acetonitrile is a better cosolvent that can be used for enhancing the transport parameters of imidazolium based RTILs for electrochemical and other applications. The results are explained in light of structure-composition-property relations and ion-ion and ion-cosolvent interactions.     

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.     

Synthesis of novel Schiff base doped sol–gel silicas

Sulfonamide Schiff bases were doped uniformly in silica sol–gels prepared from liquid precursors by a fast and easy way at room temperature and processed to form xerogels. Schiff bases are efficient chelating agents, bioactive and catalytically active compounds. The structures of the newly synthesized Schiff base doped xerogels were elucidated by their physical (morphology, surface area, porosity), spectral (FTIR) and analytical (CHNSO/Si) data. The powder X-ray diffraction studies were carried out to confirm the formation of single phase. Characterization confirmed that Schiff base molecules are entrapped inside the pores as well as physically bound onto the silica surface. All Schiff base doped xerogels are stable mesoporous materials showing hydrophilic properties. Loadings of Schiff bases from 0.10 to 0.23 g/g of xerogel were obtained resulting amorphous materials. The doping of Schiff bases with xerogel caused change in surface area, pore volume and pore diameter of xerogel without damaging the main framework of siliceous skeleton. Morphology and colour of xerogel was also changed after doping. The entrapment of Schiff bases in xerogel caused increase in their decomposition temperatures. The final Schiff base doped xerogels show remarkable thermal stability.     

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.     

Effects of surfactant micelles on solubilization and DPPH radical scavenging activity of Rutin

The interaction of the antioxidant Rutin with the radical DPPH (2,2-diphenyl-1-picrylhydrazyl) in presence of cationic (CTAB, TTAB, DTAB), non-ionic (Brij78, Brij58, Brij35), anionic (SDS) and mixed surfactant systems (CTAB-Brij58, DTAB-Brij35, SDS-Brij35) has been followed by spectrophotometric and tensiometric methods to evaluate the DPPH radical scavenging activity (RSA) of Rutin in these model self-assembled structures. The results show that the solubilization capacity of various single surfactant systems for both DPPH as well as Rutin followed the order cationics > non-ionics > anionic. The radical scavenging activity of Rutin in the solubilized form was higher within ionic micelles than in non-ionic micelles. However, the antioxidant exhibited enhanced activity for the radical in mixed cationic-non-ionic micelles compared with any of the single component micelles. In contrast, anionic-non-ionic mixed micelles modulated the activity of Rutin in-between that seen for pure anionic and non-ionic micelles only.