Physical investigations on pulsed laser deposited nanocrystalline ZnO thin films

The nanocrystalline ZnO thin films were deposited by pulsed laser deposition on quartz and i-Si (100) substrates at different substrate temperatures (473 K–873 K) and at different mixed partial pressures (0.05, 0.01, and 0.5 mbar) of Ar+O₂. The structural studies from XRD spectra reveals that the films deposited at 0.05 mbar and at lower substrate temperatures were c-axis oriented with predominant (002) crystallographic orientation. At 873 K along with (002) orientation, additional crystallographic orientations were also observed in case of films deposited at 0.01 and 0.5 mbar pressures. The composition of Zinc and Oxygen in ZnO films from EDAX reveals that the films deposited at lower partial pressures were have high at.% of O₂ whereas higher partial pressures and substrate temperatures had high at.% Zn. The surface microstructure of the films show that the films deposited at lower partial pressures (0.05 mbar ) and at lower substrate temperatures (473 K) were found to have nanoparticles of size 15 nm where as films deposited at 873 K have nanorods. The length of these nanorods increases with increasing Ar+O₂ partial pressure to 0.5 mbar. The optical energy gap of the film deposited at lower partial pressure and substrate temperature was 3.3 eV and decrease with the increase of substrate temperatures. The films deposited at 0.5 mbar and at 873 K emitted an intense luminescence at a wavelength of 390 nm. The measured thickness of deposited films by spectroscopic ellipsometry is around 456 nm.     

Applications of high resolution spectroscopy to the identification of far-infrared laser emission from optically pumped13CH3OH

High-resolution infrared (IR) and far infrared (FIR) Fourier transform absorption spectra have been employed to investigate assignments of FIR laser lines reported from optically-pumped¹³CH₃OH. The spectroscopic measurements are used in conjunction with the reported IR pump and FIR laser frequencies to form closed combination loops for several systems, serving to confirm the assignments and in some cases to improve the accuracy of the FIR laser frequencies. Frequency predictions from combination differences are also presented for a number of potential new FIR laser lines.     

Arsenic(III) sorption on nanostructured cerium incorporated manganese oxide (NCMO): a physical insight into the mechanistic pathway

Arsenic(III) sorption was investigated with nanostructured cerium incorporated manganese oxide (NCMO). The pH between 6.0 and 8.0 was optimized for the arsenic(III) sorption. Kinetics and equilibrium data (pH=7.0±0.2, T=303±1.6 K, and I=0.01 M) of arsenic(III) sorption by NCMO described, respectively, the pseudo-second order and the Freundlich isotherm equations well. The sorption process was somewhat complicated in nature and divided into two different segments, initially very fast sorption followed by slow intraparticle diffusion process. Sorption reaction of arsenic(III) on NCMO was endothermic (ΔH°=+13.46 kJ mol(-1)) and spontaneous (ΔG°=-24.75 to -30.15 kJ mol(-1) at T=283-323 K), which took place with increasing entropy (ΔS°=+0.14 kJ mol(-1)K(-1)) at solid-liquid interface. Energy of arsenic(III) sorption estimated by analyzing the equilibrium data using the D-R isotherm model was 15.4 kJ mol(-1), indicating the ion-exchange type mechanism. Raman, FT-IR, pH effect, desorption, etc. studies indicated that arsenic(III) was oxidized to arsenic(V) during the sorption process.     

A Rapid and Simple UPLC-MS–MS based Simultaneous Determination of the Medicinally Important E- and Z-Guggulsterone from Oleogum-Resins of Naturally Occurring Commiphora wightii Plants

A fast and simple method for simultaneous detection and quantification of the medicinally important E- and Z-guggulsterone from raw oleogum-resin of Commiphora wightii by UPLC was developed. Both E- and Z-guggulsterone were extracted from naturally occurring resin samples using ethyl acetate and methanol. Chromatographic separation of the analytes and their respective standards were performed on an Acquity UPLC BEH C₁₈ column followed by UV as well as a triple quadrupole detector in positive ionization mode. A linear gradient elution profile followed; mobile phase consisted of acetonitrile and 2 mM ammonium acetate in water. The method was validated over a range of 6.25 to 100 ng mL⁻¹ for both the guggulsterones. The calibration curves were linear with correlation coefficients of 0.9998 for E-guggulsterone and 0.9999 for Z-guggulsterone. The LOD and LOQ were 1.65 and 5.02 ng mL⁻¹ for E-guggulsterone and 2.57 and 7.79 ng mL⁻¹ for Z-guggulsterone respectively. The average recovery of E-guggulsterone (104.63%) and Z-guggulsterone (104.33%) achieved from spiked samples were consistent and reproducible. The intra- and inter-day assay precision of the analytes over the entire concentration range was less than 2%. The developed method required only 6 min to complete a run including 1 min to equilibrate the system and hence suitable for high throughput applications. Efficiency, reliability and accuracy of the developed method were evaluated by analyzing resin sample from different C. wightii populations. The result of this study offers improvement in terms of speed and sensitivity as compared to previously reported methods.

     

Numerical study of concentrated fluid–particle suspension flow in a wavy channel

The particle migration effects and fluid–particle interactions occurring in the flow of highly concentrated fluid–particle suspension in a spatially modulated channel have been investigated numerically using a finite volume method. The mathematical model is based on the momentum and continuity equations for the suspension flow and a constitutive equation accounting for the effects of shear‐induced particle migration in concentrated suspensions. The model couples a Newtonian stress/shear rate relationship with a shear‐induced migration model of the suspended particles in which the local effective viscosity is dependent on the local volume fraction of solids. The numerical procedure employs finite volume method and the formulation is based on diffuse‐flux model. Semi‐implicit method for pressure linked equations has been used to solve the resulting governing equations along with appropriate boundary conditions. The numerical results are validated with the analytical expressions for concentrated suspension flow in a plane channel. The results demonstrate strong particle migration towards the centre of the channel and an increasing blunting of velocity profiles with increase in initial particle concentration. In the case of a stenosed channel, the particle concentration is lowest at the site of maximum constriction, whereas a strong accumulation of particles is observed in the recirculation zone downstream of the stenosis. The numerical procedure applied to investigate the effects of concentrated suspension flow in a wavy passage shows that the solid particles migrate from regions of high shear rate to low shear rate with low velocities and this phenomenon is strongly influenced by Reynolds numbers and initial particle concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

A new multi-objective genetic algorithm applied to hot-rolling process

A new genetic algorithms based multi-objective optimization algorithm (NMGA) has been developed during study. It works on a neighborhood concept in the functional space, utilizes the ideas on weak dominance and ranking and uses its own procedures for population sizing. The algorithm was successfully tested with some standard test functions, and when applied to a real-life data of the hot-rolling campaign of an integrated steel plant, it outperformed another recently developed multi-objective evolutionary algorithm.     

Cascade synthesis of selective dihydro pyridazino fused acridinone derivatives via MCM-41 catalyzed ring-opening/ring-closure reaction

An enhanced one-pot synthesis of new functionalized 5,6-dihydro-5,5-dimethyl-2-phenyl-2H-pyridazino[3,4,5-kl]acridin-1(4H)-one derivatives with different substituted patterns by using mesoporous MCM-41 catalyst via a ring opening/ring closure reaction process has been established. This MCM-41 silica catalyst has been synthesized and characterized using an array of sophisticated analytical techniques like BET, XRD, UHRTEM, etc. This reaction could be conducted from inexpensive substrates within short period under neat reflux conditions. Compared with the usual methods, the remarkable advantages of this method are milder reaction conditions, operational simplicity, higher yields, short reaction times and an environmentally friendly procedure.     

Kinetics of Surfactant-induced Aggregation of Lysozyme Studied by Fluorescence Spectroscopy

The study of protein conformational changes in the presence of surfactants and lipids is important in the context of protein folding and misfolding. In the present study, we have investigated the mechanism of the protein conformational change coupled with aggregation leading to size growth of Hen Egg White Lysozyme (HEWL) in the presence of an anionic detergent such as sodium dodecyl sulphate (SDS) in alkaline pH. We have utilized intrinsic protein fluorescence (tryptophan) and extrinsic fluorescent reporters such as 8-anilinonaphthalene-1-sulfonic acid (ANS), dansyl and fluorescein to follow the protein conformational change in real-time. By analyzing the kinetics of fluorescence intensity and anisotropy of multiple fluorescent reporters, we have been able to delineate the mechanism of surfactant-induced aggregation of lysozyme. The kinetic parameters reveal that aggregation proceeds with an initial fast-phase (conformational change) followed by a slow-phase (self-assembly). Our results indicate that SDS, below critical micelle concentration, induces conformational expansion that triggers the aggregation process at a micromolar protein concentration range.     

Spin-density wave near the vortex cores in the high-temperature superconductor Bi2Sr2CaCu2O8+y

Competition with magnetism is at the heart of high-temperature superconductivity, most intensely felt near a vortex core. To investigate vortex magnetism we have developed a spatially resolved probe based upon NMR spin-lattice-relaxation spectroscopy. With this approach we have found a spin-density wave associated with the vortex core in Bi(2)Sr(2)CaCu(2)O(8+y), similar to checkerboard patterns in the local density of electronic states reported from scanning tunneling microscope experiments. We have determined both the spin-modulation amplitude and decay length from the vortex core in fields up to H=30 T.     

Experimental studies of the jamming behaviour of triblock copolymer solutions and triblock copolymer-anionic surfactant mixtures

Photon correlation spectroscopy and rheological measurements are performed to investigate the microscopic dynamics and mechanical responses of aqueous solutions of triblock copolymers and aqueous mixtures of triblock copolymers and anionic surfactants. Increasing the concentration of triblock copolymers results in a sharp increase in the magnitude of the complex moduli characterising the samples. This is understood in terms of the changes in the aggregation and packing behaviours of the copolymers and the constraints imposed upon their dynamics due to increased close packing. The addition of suitable quantities of an anionic surfactant to a strongly elastic copolymer solution results in a decrease in the complex moduli of the samples by several decades. It is argued that the shape anisotropy and size polydispersity of the micelles comprising mixtures cause dramatic changes in the packing behaviour, resulting in sample unjamming and the observed decrease in complex moduli. Finally, a phase diagram is constructed in the temperature-surfactant concentration plane to summarise the jamming-unjamming behaviour of aggregates constituting triblock copolymer-anionic surfactant mixtures.