Voltammetric determination of nitroaromatic and nitramine explosives contamination in soil

The contamination of soil by nitroaromatic and nitramine explosives is widespread during the manufacture, testing and disposal of explosives and ammunitions. The analysis for the presence of trace explosive contaminants in soil becomes important in the light of their effect on the growth of different varieties of plants and crops. 2,4,6-Trinitrotoluene (TNT), cyclotrimethylene trinitramine (Research Department explosive, RDX) and cyclotetramethylene tetranitramine (high melting point explosive, HMX), other related explosive compounds and their by-products must be monitored in soil and surrounding waterways since these are mutagenic, toxic and persistent pollutants that can leach from the contaminated soil to accumulate in the food chain. In this study, a voltammetric method has been developed for the determination of explosive such as RDX, HMX and TNT. The electrochemical redox behavior of RDX, HMX and TNT was studied through cyclic voltammetry and quantitative determination was carried out by using square wave voltammetry technique. Calibration curves were drawn and were linear in the range of 63-129 ppm for RDX with a detection limit of 10 ppm, 49-182 ppm for HMX with a detection limit of 1 ppm and 38-139 ppm for TNT with a detection limit of 1 ppm. This method was applied to determine the contaminations in several soil samples that yielded a relative error of 1% in the concentrations.     

A chemical genetic screen for direct v-Src substrates reveals ordered assembly of a retrograde signaling pathway

Using an ATP analog that is a specific substrate for an analog-specific allele of v-Src, we identified several novel cytoskeletal substrates that control actin assembly processes. A screen for less abundant v-Src substrates revealed the scaffolding protein Dok-1 as a direct substrate of v-Src. Further studies suggest that v-Src phosphorylation sites on Dok-1 are critical for its binding to RasGAP and Csk, negative regulators of Src signaling. This results in the downregulation of growth-promoting signals of the Src family kinases and the Ras pathway. Identification of the direct substrates of v-Src leads to a model for the precise order of assembly of a retrograde signaling pathway in v-Src-transformed cells and has provided new insight into the balance between those signals that promote cell transformation mediated by v-Src catalyzed tyrosine phosphorylation and those that inhibit it.     

Spectral characteristics of intense red luminescence in Pr:Y2O3 nanophosphor on UV excitation

Detailed structural and spectroscopic characterizations of Pr:Y₂O₃ nanophosphor have been carried out. On ultraviolet light (at 266?nm) excitation, intense red emission along with weak emissions in blue, green and infrared regions have been observed. The phenomena for the observed emission have been thoroughly explained in the present work and it was finally concluded that the?direct excitation through low-lying 4f¹5d band of Pr³⁺ ions and through the conduction band of Y₂O₃ nanophosphor are the main channels for the observed emissions. The calculated quantum efficiency (QE) for the red emission is found to be ~80?% while the CIE coordinates are (0.65, 0.34) quite close to the standard values. These studies clearly indicate that Pr:Y₂O₃ nanophosphors are promising and futuristic red luminescent material for the development of various display devices and UV detectors. Time resolved spectroscopy has been further used to investigate luminescence dynamics.     

Anomalous variation of the Lamb-M?ssbauer factor at the magnetic transition temperature in magnetoelectric?GaFeO(3)

Temperature-dependent (57)Fe M?ssbauer spectroscopy (5-723?K) and neutron diffraction (2-290?K) measurements are carried out on polycrystalline magnetoelectric GaFeO(3). From the neutron diffraction data, evidence for the magnetostriction and increased disorder at Fe sites close to the ferrimagnetic Curie transition temperature (T(C)) is observed. From the M?ssbauer data, it is observed that the Lamb-M?ssbauer factor as a function of temperature f(T), which is related to the integral over the first Brillouin zone of the phonon spectrum, shows a unequivocal variation at the T(C). The observations are discussed in terms of spin-phonon coupling. The observed average hyperfine fields from (57)Fe M?ssbauer spectra match with the bulk magnetization data. A critical exponent (β) of 0.38?±?0.02 and a Debye temperature (θ(D)) of ～350?K is estimated from the (57)Fe M?ssbauer data.     

Chiral discrimination by hydrolytic enzymes in the synthesis of optically pure materials

Enantioselection effected by commercially available hydrolytic enzymes reported in recent years from our own laboratory and those published by other groups is described. The discussion is confined to enantioselection in symmetric diols, amino acids and benzopyran derivatives only. The paper describes a variety of substrates accepted by these hydrolytic enzymes to produce compounds in high enantiomeric excess which can be used as chiral building blocks for the synthesis of compounds of pharmaceutical and synthetic interest.     

Structural and dynamical aspects of PEG/LiClO4 in solvent mixtures via NMR spectroscopy

Motivated by the potential usefulness of polyethylene glycol (PEG)/Li⁺ salt mixtures in several industrial applications, we investigated the structure and dynamics of PEG/LiClO₄ mixtures in D₂O and its mixtures with CD₃CN and DMSO-d₆, in a series of PEG-based polymers with a wide variation in their molecular weights. ¹H NMR chemical shifts, T₁/T₂ relaxation rates, pulsed-field gradient NMR diffusion experiments, and 2D HOESY NMR studies have been performed to understand the structural and dynamical aspects of these mixtures. Increasing the temperature of the medium results in a significant perturbation in the H-bonded structure of PEG in its PEG/LiClO₄/D₂O mixtures as observed from the increase in chemical shifts. On the other hand, the addition of molecular cosolvents has a negligible effect. The hydrodynamic structure of PEG shows a pronounced variation at low temperature with increasing molecular weight, which, however, disappears at higher temperatures. Increasing the temperature leads to a decrease in the hydrodynamic structure of PEG, which can be explained on the basis of solvation–desolvation phenomena. The 2D HOESY NMR spectra reveal a new finding of Li⁺-water binding in the PEG/LiClO₄/D₂O mixtures with the addition of molecular solvents, suggesting that the Li⁺ cation diffuses freely in the D₂O mixtures of polymers as compared with the polymer mixtures with DMSO or CD₃CN.     

Experimental detection of qubit-ququart pseudo-bound entanglement using three nuclear spins

In this work, we experimentally created and characterized a class of qubit-ququart PPT (positive under partial transpose) entangled states using three nuclear spins on an nuclear magnetic resonance (NMR) quantum information processor. Entanglement detection and characterization for systems with a Hilbert space dimension $\ge 2?3$ is nontrivial since there are states in such systems which are both PPT as well as entangled. The experimental detection scheme that we devised for the detection of qubit-ququart PPT entanglement was based on the measurement of three Pauli operators with high precision, and is a key ingredient of the protocol in detecting entanglement. The family of PPT-entangled states considered in the current study are incoherent mixtures of five pure states. All the five states were prepared with high fidelities and the resulting PPT entangled states were prepared with mean fidelity ≥ 0.95. The entanglement thus detected was validated by carrying out full quantum state tomography (QST).