Potentiometric titration in a low volume of solution for rapid assay of uranium: application to quantitative electro-reduction of uranium(VI)

A simple, inexpensive PC based potentiometric titration technique for the assay of uranium using low volumes of sample aliquot (25–100 μL) along with all reagents (total volume of solution being less than 2.5 mL) is presented. The technique involves modification of the well known Davies and Gray Method recommended for assay of uranium(VI) in nuclear materials by introducing an innovative potentiometric titration device with a mini cell developed in-house. After appropriate chemical conditioning the titration is completed within a couple of minutes with display of online titration plot showing the progress of titration. The first derivative plot generated immediately after titration provides information of end point. The main advantage of using this technique is to carry out titration with minimum volumes of sample and reagents generating minimum volume of wastes after titration. The validity of the technique was evaluated using standard certified samples. This technique was applied for assay of uranium in a typical sample collected from fuel reprocessing laboratory. Further, the present technique was deployed in investigating the optimum conditions for efficient in situ production of U(IV). The precision in the estimation of uranium is highly satisfactory (RSD less than 1.0%).     

Plasma Synthesis of Advanced Metal Oxide Nanoparticles and Their Applications as Transparent Conducting Oxide Thin Films

This article reviews and summarizes work recently performed in this laboratory on the synthesis of advanced transparent conducting oxide nanopowders by the use of plasma. The nanopowders thus synthesized include indium tin oxide (ITO), zinc oxide (ZnO) and tin-doped zinc oxide (TZO), aluminum-doped zinc oxide (AZO), and indium-doped zinc oxide (IZO). These oxides have excellent transparent conducting properties, among other useful characteristics. ZnO and TZO also has photocatalytic properties. The synthesis of these materials started with the selection of the suitable precursors, which were injected into a non-transferred thermal plasma and vaporized followed by vapor-phase reactions to form nanosized oxide particles. The products were analyzed by the use of various advanced instrumental analysis techniques, and their useful properties were tested by different appropriate methods. The thermal plasma process showed a considerable potential as an efficient technique for synthesizing oxide nanopowders. This process is also suitable for large scale production of nano-sized powders owing to the availability of high temperatures for volatilizing reactants rapidly, followed by vapor phase reactions and rapid quenching to yield nano-sized powder.     

Genotoxic and Cytotoxic Properties of Zinc Oxide Nanoparticles Phyto-Fabricated from the Obscure Morning Glory Plant Ipomoea obscura (L.) Ker Gawl

The study was undertaken to investigate the antioxidant, genotoxic, and cytotoxic potentialities of phyto-fabricated zinc oxide nanoparticles (ZnO-NPs) from Ipomoea obscura (L.) Ker Gawl. aqueous leaf extract. The UV-visible spectral analysis of the ZnO-NPs showed an absorption peak at 304 nm with a bandgap energy of 3.54 eV, which are characteristics of zinc nanoparticles. Moreover, the particles were of nano-size (~24.26 nm) with 88.11% purity and were agglomerated as observed through Scanning Electron Microscopy (SEM). The phyto-fabricated ZnO-NPs offered radical scavenging activity (RSA) in a dose-dependent manner with an IC₅₀ of 0.45 mg mL⁻¹. In addition, the genotoxicity studies of ZnO-NPs carried out on onion root tips revealed that the particles were able to significantly inhibit the cell division at the mitotic stage with a mitotic index of 39.49%. Further, the cytotoxic studies on HT-29 cells showed that the phyto-fabricated ZnO-NPs could arrest the cell division as early as in the G0/G1 phase (with 92.14%) with 73.14% cells showing early apoptotic symptoms after 24 h of incubation. The results of the study affirm the ability of phyto-fabricated ZnO-NPs from aqueous leaf extract of I. obscura is beneficial in the cytotoxic application.     

Phase stabilisation of blue-phase liquid crystals using a polymerisable chiral additive

We report a novel polymer stabilisation of blue phase by a chiral agent itself without additional reactive monomers. In this way, the structural difference in phase stabilisation gives rise to novel electro-optic properties such as the hysteresis-free with low-operating voltages. The number of constituents in polymer-stabilised blue-phase mixture is reduced and the polymer network more directly engages the structure of the blue phase, so that the hysteresis is free with less contamination for liquid crystals to be rearranged by electric fields. Also, relatively low operating voltage is achieved because the chiral pitch becomes longer owing to the chiral agent becoming polymerised. This result would open up an innovative way from a material perspective on stabilisation of blue-phase liquid crystals.     

Identification of degradation impurities in aripiprazole oral solution using LC–MS and development of validated stability indicating method for assay and content of two preservatives by RP-HPLC

A simple and simultaneous reverse phase high-performance liquid chromatographic method was developed for the quantification of aripiprazole (ARI) and two preservatives, namely, methyl paraben and propyl paraben in ARI oral solution. The method was developed on ACE C18 (4.6?×?250?mm, 5?µm) column using gradient elution of 0.1% v/v trifluoroacetic acid in water and acetonitrile as mobile phase components. Flow rate of 1.0?mL/min and 30°C column temperature were used for the method at quantification wavelength of 254?nm. The developed method was validated in accordance with International Conference on Harmonization guideline for various parameters. Forced degradation study was conducted in acid, base, peroxide, heat, and light stress conditions. ARI was found to degrade in oxidation, acid hydrolysis, and heat while it was stable under the remaining conditions. Specificity of the method was verified using Photo Diode Array (PDA) detector by evaluating purity of peaks from degradation samples. Major degradation impurities formed during stress study were identified using liquid chromatography–mass spectrometry method. The present method was useful for determining the content of all the three main analytes present in the oral solution without interference from degradation impurities. The method was robust under the deliberately modified conditions.     

Autofluorescence of oral tissue for optical pathology in oral malignancy

Pulsed laser-induced-fluorescence studies of pathologically certified oral tissues are carried out at different excitations and time delays. Among the several excitations used, 325 nm produced noticeably different spectral profile for normal and malignant tissues. Extensive curve analysis was carried out in order to understand changes in biochemical composition of tissue based on spectral profiles. Curve resolution and principal component analysis (PCA) show that the fluorescence intensity changes from normal to malignant tissue samples are not completely explained in terms of simple collagen and NAD(P)H intensity changes. The spectra require at least five components to be fully accounted for. Several discrimination methodologies based on PCA and intensity differences between different emission peaks (resultant peaks of curve analysis) were also evaluated. The results obtained indicate PCA using Mahalanobis distance and spectral residual as discrimination parameters provides best discrimination and can be used for matching unknown samples to standard calibration sets. Intensity ratio of bound NAD(P)H to collagen seems to be more suitable for discrimination between normal and malignant oral tissue, compared to ratio of collagen to total intensity of all the other components together.     

Characterization of dihydrostreptomycin‐related substances by liquid chromatography coupled to ion trap mass spectrometry

Dihydrostreptomycin sulphate (DHS) is a water‐soluble, broad‐spectrum aminoglycoside antibiotic. For quantitative analysis, the European Pharmacopoeia (Ph. Eur.) prescribes an ion‐pairing liquid chromatography/ultraviolet (LC/UV) method using a C18 stationary phase. Several unknown compounds were detected in commercial samples. Hence, for characterization of these unknown peaks in a commercial DHS sample, the Ph. Eur. method was coupled to mass spectrometry (MS). However, since the Ph. Eur. method uses a non‐volatile mobile phase, each peak eluted was collected and desalted before introduction into the mass spectrometer. The desalting procedure was applied to remove the non volatile salt, buffer and ion‐pairing reagent in the collected fraction. In total, 20 impurities were studied and 14 of them were newly characterized. Five impurities which are already reported in the literature were also traced in this LC/UV method. Copyright © 2009 John Wiley & Sons, Ltd.     

Engineering of CH3NH3PbI3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties

The number of studies on organic–inorganic hybrid perovskites has soared in recent years. However, the majority of hybrid perovskites under investigation are based on a limited number of organic cations of suitable sizes, such as methylammonium and formamidinium. These small cations easily fit into the perovskite's three‐dimensional (3D) lead halide framework to produce semiconductors with excellent charge transport properties. Until now, larger cations, such as ethylammonium, have been found to form 2D crystals with lead halide. Here we show for the first time that ethylammonium can in fact be incorporated coordinately with methylammonium in the lattice of a 3D perovskite thanks to a balance of opposite lattice distortion strains. This inclusion results in higher crystal symmetry, improved material stability, and markedly enhanced charge carrier lifetime. This crystal engineering strategy of balancing opposite lattice distortion effects vastly increases the number of potential choices of organic cations for 3D perovskites, opening up new degrees of freedom to tailor their optoelectronic and environmental properties.