On‐line extraction and determination of two herbicides: Comparison between two modes of three‐phase hollow fiber microextraction

Two different modes of three‐phase hollow fiber liquid‐phase microextraction were studied for the extraction of two herbicides, bensulfuron‐methyl and linuron. In these two modes, the acceptor phases in the lumen of the hollow fiber were aqueous and organic solvents. The extraction and determination were performed using an automated hollow fiber microextraction instrument followed by high‐performance liquid chromatography. For both three‐phase hollow fiber liquid‐phase microextraction modes, the effect of the main parameters on the extraction efficiency were investigated and optimized by central composite design. Under optimal conditions, both modes showed good linearity and repeatability, but the three‐phase hollow fiber liquid‐phase microextraction based on two immiscible organic solvents has a better extraction efficiency and figures of merit. The calibration curves for three‐phase hollow fiber liquid‐phase microextraction with an organic acceptor phase were linear in the range of 0.3–200 and 0.1–150 μg/L and the limits of detection were 0.1 and 0.06 μg/L for bensulfuron‐methyl and linuron, respectively. For the conventional three‐phase hollow fiber liquid‐phase microextraction, the calibration curves were linear in the range of 3.0–250 and 15–400 μg/L and LODs were 1.0 and 5.0 μg/L for bensulfuron‐methyl and linuron, respectively. The real sample analysis was carried out by three‐phase hollow fiber liquid phase microextraction based on two immiscible organic solvents because of its more favorable characteristics.     

Chemical sensing in two dimensional porous covalent organic nanosheets

Two new imide-based crystalline, porous, and chemically stable covalent organic frameworks (COFs) (TpBDH and TfpBDH) have been successfully synthesized employing solvothermal crystallization route. Furthermore, thin layered covalent organic nanosheets (CONs) were derived from these bulk COFs by the simple liquid phase exfoliation method. These 2D CONs showcase increased luminescence intensity compared to their bulk counterparts (COFs). Notably, TfpBDH-CONs showcase good selectivity and prominent, direct visual detection towards different nitroaromatic analytes over TpBDH-CONs. Quite interestingly, TfpBDH-CONs exhibit a superior “turn-on” detection capability for 2,4,6-trinitrophenol (TNP) in the solid state, but conversely, they also show a “turn-off” detection in the dispersion state. These findings describe a new approach towards developing an efficient, promising fluorescence chemosensor material for both visual and spectroscopic detection of nitroaromatic compounds with very low [10^–5 (M)] analyte concentrations.     

Real‐Time Band‐Selective Homonuclear Proton Decoupling for Improving Sensitivity and Resolution in Phase‐Sensitive J‐Resolved Spectroscopy

Real‐time band‐selective homonuclear ¹H decoupling during data acquisition of z‐filtered J‐resolved spectroscopy produces ¹H‐decoupled ¹H NMR spectra and leads to sensitivity enhancement and improved resolution, and thus aids the measurement of J couplings and residual dipolar couplings in crowded regions of ¹H NMR spectrum. High quality spectra from peptides, organic molecules, and also from enantiomers dissolved in weakly aligned chiral media are reported.     

Morphogenetic and chemical stability of long-term maintained Agrobacterium-mediated transgenic Catharanthus roseus plants

Transgenic Catharanthus roseus plants (transgenic Dhawal [DT] and transgenic Nirmal [NT]) obtained from the Agrobacterium tumefaciens and Agrobacteriumrhizognenes-mediated transformations, respectively, have been maintained in vitro for 5 years. Plants were studied at regular intervals for various parameters such as plant height, leaf size, multiplication rate, alkaloid profile and presence of marker genes. DT plant gradually lost the GUS gene expression and it was not detected in the fifth year while NT plant demonstrated the presence of genes rolA, rolB and rolC even in the fifth year, indicating the more stable nature of Ri transgene. Vindoline content in the DT was two times more than in non-transformed control plants. Alkaloid and tryptophan profiles were almost constant during the 5 years. The cluster analysis revealed that the DT plant is more close to the control Nirmal plant followed by NT plant.     

Degradation kinetics of pollutants present in a simulated wastewater matrix using UV/TiO<Subscript>2</Subscript> photocatalysis and its microbiological toxicity assessment

Water pollution is one of the major concerns over long-term sustainability of the environment. Effective and efficient treatment of polluted wastewater is still a serious challenge for global researchers. In the last 2–3 decades, due to the incessant emergence of micropollutants in surface and ground water bodies, several endeavors have been made to resolve the water pollution issues either through chemical, physical and biological degradation processes or through removal/separation processes using different adsorbents and membranes. It has been found that most of the studies are mainly limited to single or binary pollutant analysis in a pure water matrix. Therefore, in this novel investigation, a mixture of five different pollutants has been studied for UV/TiO₂-based photocatalytic degradation. In the present study, a commercially available TiO₂, an antibiotic, i.e. Ciprofloxacin and four different synthetic dyes, i.e. Rhodamine B, Methylene Blue, Methyl Orange and Amaranth have been used as a photocatalyst, a pharmaceutical and various industrial dyes, respectively, in a batch photocatalytic reactor system with a stirrer. It is important to note that the commercial TiO₂ photocatalyst has also been characterized with the help of several characterization techniques. The present study is mainly focused on the degradation of different micropollutants present in the simulated wastewater matrix and their individual degradation kinetics. It is interesting to observe that MB and RhB have shown the maximum degradation followed by CIP (96.21, 96.15 and 89.62%, respectively). In addition, a microbiological assay has also been performed to check the toxicity variation in the degraded products. It is quite interesting to observe that the simulated wastewater matrix has completely lost its microbial toxicity within 120 min of UV/TiO₂-based photocatalytic treatment. Finally, total organic carbon evaluations of various treated samples have also been performed and the obtained results substantiate the theory of assimilable organic carbon.     

Strategies for enhanced photodynamic therapy effects

Photodynamic therapy (PDT) is a treatment modality for the selective destruction of cancerous and nonneoplastic pathologies that involves the simultaneous presence of light, oxygen and a light-activatable chemical called a photosensitizer (PS) to achieve a cytotoxic effect. The photophysics and mechanisms of cell killing by PDT have been extensively studied in recent years, and PDT has received regulatory approval for the treatment of a number of diseases worldwide. As the application of this treatment modality expands with regard to both anatomical sites and disease stages, it will be important to develop strategies for enhancing PDT outcomes. This article focuses on two broad approaches for PDT enhancement: (1) mechanism-based combination treatments in which PDT and a second modality can be designed to either increase the susceptibility of tumor cells to PDT or nullify the treatment outcome-mitigating molecular responses triggered by PDT of tumors, and (2) the more recent approaches of PS targeting, either by specific cellular function-sensitive linkages or via conjugation to macromolecules.     

Determination of trace amounts of nitrogen in uranium based samples by ion chromatography (IC) without Kjeldahl distillation

A simple, sensitive and fast ion chromatographic (IC) method with suppressed conductivity detection is described for the determination of traces of nitrogen in uranium based fuel materials. Initially a method was developed to determine nitrogen as NH₄⁺ using cation exchange column after matrix separation by Kjeldahl distillation. The method was then improved by eliminating this distillation. Matrix separation after sample dissolution was done by hydrolyzing and filtering off the polyvalent cations. This had helped in reducing both the sample size and analysis time. Optimization of dissolution conditions for various kinds of uranium based samples was done to keep acid content minimum; a prerequisite chromatographic condition. The calibration plot for nitrogen was linear in the concentration range of 0.02-1 mg L⁻¹ with regression coefficient of 0.9999. The relative standard deviation (R.S.D.) obtained in this method (100 μL injected) was 3% and 2% in 9 replicates at nitrogen level of 28 and 55 ng g⁻¹, respectively. Detection limit based on S/N = 3 (100 μL injected) as well as three times of variation in blank value was 4 ng g⁻¹. The developed method was authenticated by comparison with certified uranium-alloy standard as well as with independent indophenol photometry method. The developed method was applied to uranium-alloy, uranium-metal, sintered UO₂ pellets and sintered UO₂ microspheres samples.     

Close contacts between carbonyl oxygen atoms and aromatic centers in protein structures: pi...pi or lone-pair...pi interactions?

Lone-pair...pi and, more recently, pi...pi interactions have been studied in small molecule crystal structures, and they are the focus of attention in some biomolecules. In this study, we have systematically analyzed 500 high-resolution protein structures (resolution < or =1.8 A) and identified 286 examples in which carbonyl oxygen atoms approach the aromatic centers within a distance of 3.5 A. Contacts involving backbone carbonyl oxygens are frequently observed in helices and, to some extent, in strands. Geometrical characterization indicates that these contacts have geometry in between that of an ideal pi...pi and a lone-pair...pi interaction. Quantum mechanical calculations using 6-311++G** basis sets reveal that these contacts give rise to energetically favorable interactions and, along with MD simulations, indicate that such interactions could stabilize secondary structures.     

A bounded convection scheme for the overlapping control volume approach

This paper introduces a flux-limited scheme FLOCV for the overlapping control volume (OCV) approach to 2D steady and unsteady convection–diffusion problems on structured non-orthogonal grids. FLOCV switches from second- to first-order interpolation in the presence of extrema. Smooth switching between the two is ensured by weighted average second- and first-order upwind differencing, with the weights being dynamically determined. Five convective test problems are solved using this scheme and results are compared with known analytical solutions. It is found that FLOCV approximately retains second-order accuracy of the base discretization scheme on uniform grids and smooth non-uniform orthogonal grids. It is also found effective in removing oscillations for problems with discontinuities on both orthogonal and non-orthogonal grids, with little degradation of accuracy. © 1997 John Wiley & Sons, Ltd.     

Preparation and characterization of chemically deposited (Cd0.7‐Zn0.3)S:CdCl2,Gd nanocrystalline films

Nanocrystalline films of (Cd_0.7‐Zn_0.3)S:CdCl₂,Gd are prepared by chemical deposition technique on microscopic glass substrates with varied concentrations of capping agents thiophenol and methanol. The deposition is based on the principle of precipitation followed by condensation. Results of XRD, SEM, optical absorption spectra and photoluminescence emission spectra are presented. The crystalline nature of (Cd_0.7‐Zn_0.3)S:CdCl₂,Gd was found by XRD studies in which different diffraction peaks of CdS and ZnS are observed. The SEM micrographs show long tubes and irregular distributions of particles in presence of capping agents. The blue shift observed from optical absorption spectra in the present case indicates a quantization effect. Band gaps are also found to increase due to particle size reduction. The photoluminescence emission spectra show shift of peaks in the lower wavelength side due to reduction in particle size. The particle sizes are determined from optical absorption and XRD studies. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)