A theoretical charge density study on nitrogen-rich 4,4′,5,5′-tetranitro-2,2′-bi-1H-imidazole (TNBI) energetic molecule

The bond topological and electrostatic properties of nitrogen-rich 4,4′,5,5′-tetranitro-2,2′-bi-1H-imidazole (TNBI) energetic molecule have been calculated from the DFT method with the basis set 6-311G** and the AIM theory. The optimized geometry of this molecule is almost matched with the experimental geometric parameters. The electron density at the bond critical point and the Laplacian of electron density of C–NO₂ bonds are not equal, one of them is much weaker than the other. Similar trend exists in the C–N bonds of the imidazole ring of the molecule. The ratio of the bond dissociation energy (BDE) of the weakest bond to the molecular total energy exhibits nearly a linear correlation with the impact sensitivity; its h ₅₀% value is ~32.01 cm. The electrostatic potential around both the nitro groups are found unequal; the NO₂ group of weakest C–NO₂ bond exhibits an extended electronegative region.     

Multicolored and white-light phosphors based on doped GdF3 nanoparticles and their potential bio-applications

Rare-earth-doped gadolinium fluoride nanocrystals were synthesized by a single step synthesis employing ethylene glycol as solvent. Based on X-ray diffraction studies, stabilization of hexagonal modification of GdF(3) has been inferred. The microscopic studies show formation of uniformly distributed nanocrystals (~15 nm). The nanoparticles are readily dispersible in water and show bright luminescence in colloidal solution. The luminescence properties have been investigated as a function of activator concentrations, and enhanced optical properties have been attributed to efficient energy transfer from the Gd(3+) to the activator RE(3+) ions, which has further been confirmed by steady-state and time-resolved optical studies. It has been demonstrated that on doping appropriate amount of activators in host GdF(3), a novel white-light-emitting phosphor is obtained with CIE co-ordinates and correlated color temperature (CCT) very close to broad daylight. This can have promising applications as phosphor for white-light ultraviolet-light-emitting diodes (UV-LEDs). Our experiments showed efficient labeling of human breast carcinoma cells (MCF-7) by Tb(3+)-doped GdF(3) nanoparticles. The fluorescence intensity was found to be dependent on the surface modifying/coating agent, and the results were validated using confocal microscopy in terms of localization of these functionalized nanoparticles.     

Biohydrogen Production from Cheese Whey Wastewater in a Two-Step Anaerobic Process

Cheese whey-based biohydrogen production was seen in batch experiments via dark fermentation by free and immobilized Enterobacter aerogenes MTCC 2822 followed by photofermentation of VFAs (mainly acetic and butyric acid) in the spent medium by Rhodopseudomonas BHU 01 strain. E. aerogenes free cells grown on cheese whey diluted to 10 g lactose/L, had maximum lactose consumption (～79%), high production of acetic acid (1,900 mg/L), butyric acid (537.2 mg/L) and H(2) yield (2.04 mol/mol lactose; rate,1.09 mmol/L/h). The immobilized cells improved lactose consumption (84%), production of acetic acid (2,100 mg/L), butyric acid (718 mg/L) and also H(2) yield (3.50 mol/mol lactose; rate, 1.91 mmol/L/h). E. aerogenes spent medium (10 g lactose/L) when subjected to photofermentation by free Rhodopseudomonas BHU 01 cells, the H(2) yield reached 1.63 mol/mol acetic acid (rate, 0.49 mmol/L/h). By contrast, immobilized Rhodopseudomonas cells improved H(2) yield to 2.69 mol/mol acetic acid (rate, 1.87 mmol/L/h). The cumulative H(2) yield for free and immobilized bacterial cells was 3.40 and 5.88 mol/mol lactose, respectively. Bacterial cells entrapped in alginate, had a sluggish start of H(2) production but outperformed the free cells subsequently. Also, the concomitant COD reduction for free cells (29.5%) could be raised to 36.08% by immobilized cells. The data suggest that two-step fermentative H(2) production from cheese whey involving immobilized bacterial cells, offers greater substrate to- hydrogen conversion efficiency, and the effective removal of organic load from the wastewater in the long-term.     

Self‐association and hydrogen bonding of propionaldehyde in binary mixtures with water and methanol investigated by concentration‐dependent polarized Raman study and DFT calculations

The Raman spectra of neat propionaldehyde [CH₃CH₂CHO or propanal (Pr)] and its binary mixtures with hydrogen‐donor solvents, water (W) and methanol (M), [CH₃CH₂CHO + H₂O] and CH₃CH₂CHO + CH₃OH] with different mole fractions of the reference system, Pr varying from 0.1 to 0.9 at a regular interval of 0.1, were recorded in the ν(CO) stretching region, 1600–1800 cm⁻¹. The isotropic parts of the Raman spectra were analyzed for both the cases. The wavenumber positions and line widths of the component bands were determined by a rigorous line‐shape analysis, and the peaks corresponding to self‐associated and hydrogen‐bonded species were identified. Raman peak at ∼1721 cm⁻¹ in neat Pr, which has been attributed to the self‐associated species, downshifts slightly (∼1 cm⁻¹) in going from mole fraction 0.9 to 0.6 in (Pr + W) binary mixture, but on further dilution it shows a sudden downshift of ∼7 cm⁻¹. This has been attributed to the low solubility of Pr in W (∼30%), which does not permit a hydrogen‐bonded network to form at higher concentrations of Pr. A significant decrease in the intensity of this peak in the Raman spectra of Pr in a nonpolar solvent, n‐heptane, at high dilution (C = 0.05) further confirms that this peak corresponds to the self‐associated species. In case of the (Pr + M) binary mixture, however, the spectral changes with concentration show a rather regular trend and no special features were observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrogen bonding in different pyrimidine–methanol clusters probed by polarized Raman spectroscopy and DFT calculations

We report on the hydrogen bonding between pyrimidine (Pd) and methanol (M) as H‐donor in this study. Hydrogen bonds between pyrimidine and methanol molecules as well as those between different methanol molecules significantly influence the spectral features at high dilution. The ring‐breathing mode ν₁ of the reference system Pd was chosen as a marker band to probe the degree of hydrogen bonding. Polarized Raman spectra in the region 970–1020 cm⁻¹ for binary mixtures of (pyrimidine + methanol) at 28 different mole fractions were recorded. A Raman line shape analysis of the isotropic Raman line profiles at all concentrations revealed three distinct spectral components at mole fractions of Pd below 0.75. The three components are attributed to three distinct groups of species: ‘free Pd’ (pd), ‘Pd with low methanol content’ (pd1) and ‘Pd with high‐methanol content’ (pd2). The two latter species differ considerably in the pattern and the strengths of the hydrogen bonds. The results of density functional theory calculations on structures and vibrational spectra of neat Pd and eight Pd/M complexes with varying methanol content support our interpretations of the experimental results. A nice spectra–structure correlation for the different cluster subgroups was obtained, similar to earlier results obtained for Pd and water. Apart from N···H and O···H hydrogen bonds between pyrimidine and methanol, O···H hydrogen bonds formed among the methanol molecules in the cluster at high methanol content also play a crucial role in the interpretation of the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

On iterative techniques for computing flow in large two-dimensional discrete fracture networks

Computation of flow in discrete fracture networks often involves solving for hydraulic head values at all intersection points of a large number of stochastically generated fractures inside a bounded domain. For large systems, this approach leads to the generation of problems involving highly sparse matrices which must be solved iteratively. Distributions of fracture lengths spanning over several orders of magnitude, and the randomness of fracture orientations and locations, lead to coefficient matrices that are devoid of any regular structure in the sparsity pattern. In addition to the rapid increase in computational effort with increase in the size of the fracture network, the spread in the distribution of fracture parameters, such as length and transmissivity, dramatically influences the convergence behavior of the system of linear equations. An overview of the discrete fracture network (DFN) methodology for computation of flow is presented along with a comparative study of various Krylov subspace iterative methods for the resulting class of sparse matrices. The rate of convergence of the iterative techniques is found to exhibit a systematic pattern with respect to changes in statistical parameters of the stochastically generated fracture networks. Salient features of the observed trends in the convergence pattern are discussed and guidelines for design of DFN algorithms are provided.     

Effect of cathode structure on neutron yield performance of a miniature plasma focus device

In this Letter we report the effect of two different cathode structures - tubular and squirrel cage, on neutron output from a miniature plasma focus device. The squirrel cage cathode is typical of most DPF sources, with an outer, tubular envelope that serves as a vacuum housing, but does not carry current. The tubular cathode carries the return current and also serves as the vacuum envelope, thereby minimizing the size of the DPF head. The maximum average neutron yield of (1.82±0.52)×¹⁰⁵ n/shot for the tubular cathode at 4 mbar was enhanced to (1.15±0.2)×¹⁰⁶ n/shot with squirrel cage cathode at 6 mbar operation. These results are explained on the basis of a current sheath loading/mass choking effect. The penalty for using a non-transparent cathode negates the advantage of the smaller size of the DPF head.     

Acoustic wave propagation in barium monochalcogenides in the B1 phase

Temperature dependence of ultrasonic attenuation due to phonon-phonon interaction and thermoelastic loss have been studied in (NaCl-type) barium monochalcogenides [BaX, X = S, Se, Te], in the temperature range 50–500 K; for longitudinal and shear modes of propagation along 〈100〉, 〈110〉, 〈111〉 directions. Second and third order elastic constants have been evaluated using electrostatic and Born repulsive potentials and taking interactions up to next nearest neighbours. Gruneisen parameters, nonlinearity constants, nonlinearity constants ratios and viscous drag due to screw and edge dislocations have also been evaluated for longitudinal and shear waves at 300 K. In the present investigation, it has been found that phonon-phonon interaction is the dominant cause for ultrasonic attenuation. The possible implications of results have been discussed. The text was submitted by the authors in English.     

Cosmic (Super)String Constraints from 21 cm Radiation

We calculate the contribution of cosmic strings arising from a phase transition in the early Universe, or cosmic superstrings arising from brane inflation, to the cosmic 21 cm power spectrum at redshifts z > or =30. Future experiments can exploit this effect to constrain the cosmic string tension G mu and probe virtually the entire brane inflation model space allowed by current observations. Although current experiments with a collecting area of approximately 1 km2 will not provide any useful constraints, future experiments with a collecting area of 10(4)-10(6) km2 covering the cleanest 10% of the sky can, in principle, constrain cosmic strings with tension G mu > or = 10(-10)-10(-12) (superstring/phase transition mass scale >10(13) GeV).     

Dissolutive Capillary Penetration with Expanding Pores and Transient Contact Angles

The penetration kinetics of a cylindrical capillary and a capillary porous body with a temporally expanding capillary radius due to reactive dissolution ahead of the liquid front is modeled under conditions where the equilibrium contact angle is not attained during at least part of the penetration process. These effects cause deviations from the predictions of the Washburn equation, with the actual penetration kinetics depending upon the rate processes involved. Copyright 2000 Academic Press.