Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts

A near‐IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen‐bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen‐bond formation signifies that hydrogen‐bond making and breaking processes are dominated by enthalpy with non‐negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen‐bond formation and from analysis of the linear enthalpy–entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration‐shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen‐bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions.     

Enhanced field emission from pulsed laser deposited nanocrystalline ZnO thin films on Re and W

Nanocrystalline ZnO thin films have been deposited on rhenium and tungsten pointed and flat substrates by pulsed laser deposition method. An emission current of 1 nA with an onset voltage of 120 V was observed repeatedly and maximum current density ∼1.3 A/cm² and 9.3 mA/cm² has been drawn from ZnO/Re and ZnO/W pointed emitters at an applied voltage of 12.8 and 14 kV, respectively. In case of planar emitters (ZnO deposited on flat substrates), the onset field required to draw 1 nA emission current is observed to be 0.87 and 1.2 V/μm for ZnO/Re and ZnO/W planar emitters, respectively. The Fowler–Nordheim plots of both the emitters show nonlinear behaviour, typical for a semiconducting field emitter. The field enhancement factor β is estimated to be ∼2.15×10⁵ cm⁻¹ and 2.16×10⁵ cm⁻¹ for pointed and 3.2×10⁴ and 1.74×10⁴ for planar ZnO/Re and ZnO/W emitters, respectively. The high value of β factor suggests that the emission is from the nanometric features of the emitter surface. The emission current–time plots exhibit good stability of emission current over a period of more than three hours. The post field emission surface morphology studies show no significant deterioration of the emitter surface indicating that the ZnO thin film has a very strong adherence to both the substrates and exhibits a remarkable structural stability against high-field-induced mechanical stresses and ion bombardment. The results reveal that PLD offers unprecedented advantages in fabricating the ZnO field emitters for practical applications in field-emission-based electron sources.     

Lepton flavour violating heavy Higgs decays within the and their detection at the LHC

Within the νMSSM, a Minimal Supersymmetric neutrino See-saw Model, Lepton Flavour Violating Higgs couplings are strongly enhanced at large tanβ (30), which can lead to BR(H⁰/A⁰→τμ)O(10⁻⁴), for M_H⁰/A⁰160 GeV. Enhancements on the production of Higgs bosons, through the gluon fusion mechanism, gg→H⁰/A⁰, and the associated production channel , whose rates grow with tanβ, as well as the mass degeneracy that occurs between the H⁰ and A⁰ states in this regime, also contribute to further the possibilities to detect a heavy Higgs signal into τμ pairs. We show that the separation of τμ Higgs events from the background at the upcoming CERN Large Hadron Collider could be done for Higgs masses up to about 600 GeV for 300 fb⁻¹ of luminosity, for large tanβ values. However, even with as little as 10 fb⁻¹ one can probe H⁰/A⁰ masses up to 400 GeV or so, if tanβ=60. Altogether, these processes then provide a new Higgs discovery mode as well as an independent test of flavour physics.     

Ionic Liquid‐Based Routes to Conversion or Reuse of Recycled Ammonium Perchlorate

New, potentially green, and efficient synthetic routes for the remediation and/or re‐use of perchlorate‐based energetic materials have been developed. Four simple organic imidazolium‐ and phosphonium‐based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride‐based parent ionic liquid. The electrochemical degradation of the hazardous perchlorate ion and its conversion to harmless chloride during electrolysis was studied using IR and ³⁵Cl NMR spectroscopies.     

Fluoride removal using lanthanum incorporated chitosan beads

Highly selective material based on naturally occurring biomaterial namely chitosan has been designed for the defluoridation of water. Lanthanum incorporated chitosan beads (LCB) were prepared using precipitation method. The synthesis was optimized by varying different synthesis parameters namely lanthanum loading, complexation and precipitation time, strength of ammonia solution used for precipitation, drying time, etc. Lanthanum incorporated chitosan beads were characterized using SEM, FTIR, XRD and EDX. Surface area of LCB was observed to be 2.76 m² g⁻¹. The equilibrium adsorption data fitted well to Langmuir adsorption isotherm and showing maximum fluoride adsorption capacity of 4.7 mg g⁻¹ with negligible lanthanum release. Kinetic study reveals that adsorption of fluoride is fast and follows pseudo-first-order kinetics. The effect of pH was also studied and the best efficiency was observed at pH 5. Presence of sulphate, nitrate and chloride marginally affected the removal efficiency, however drastic reduction in fluoride uptake was observed in the presence of carbonate and bicarbonate. Negative value of change in free energy (ΔG°) and positive value of change in entropy (ΔS°) suggest the adsorption of fluoride by LCB is feasible and spontaneous process. Positive value of change in enthalpy (ΔH°) suggests the process of fluoride adsorption is endothermic in nature. Regeneration study reveals that 1 M ammonium chloride solution appears to be the promising regeneration media showing 81.22% regeneration. The adsorption capacity of LCB was similar in fluoride-contaminated ground water collected from Dhar district of Madhya Pradesh, India, as compared to simulated water.     

Field emission investigation of single Fe-doped SnO2 wire

Tin oxide submicronwires doped with Fe element were prepared by the thermal evaporation method. Morphological and structural characterizations revealed wires with sub micron size and crystalline in nature. The field electron emission from the single Fe:SnO₂ wire was carried out in conventional field emission microscope. The Fowler–Nordheim plot obtained from I–V characteristics of the wire showed a linear behavior typical that of metal. The field enhancement factor estimated from the slope of the F–N plot is 7455 cm^?1, indicating that the field emission is from nanometric features of the emitter. A current density of 10 A/cm² has been obtained at an applied field of 4.845 × 10³ V/μm. The field emission current–time record at a current level of 1 μA for more than 3 h duration is promising for various field emissions based applications.     

Influence of electric field intensity, ionic strength, and migration distance on the mobility and diffusion in DNA surface electrophoresis

In order to increase the separation rate of surface electrophoresis while preserving the resolution for large DNA chains, e.g., genomic DNA, the mobility and diffusion of Lambda DNA chains adsorbed on flat silicon substrate under an applied electric field, as a function of migration distance, ionic strength, and field intensity, were studied using laser fluorescence microscope. The mobility was found to follow a power law with the field intensity beyond a certain threshold. The detected DNA peak width was shown to be constant with migration distance, slightly smaller with stronger field intensity, but significantly decreased with higher ionic strength. The molecular dynamics simulation demonstrated that the peak width was strongly related with the conformation of DNA chains adsorbed onto surface. The results also implied that there was no diffusion of DNA during migration on surface. Therefore, the Nernst-Einstein relation is not valid in the surface electrophoresis and the separation rate could be improved without losing resolution by decreasing separation distance, increasing buffer concentration, and field intensity. The results indicate the fast separation of genomic DNA chains by surface electrophoresis is possible.     

Behavior of nonlinear fluid viscous dampers for control of shock vibrations

Fluid viscous dampers have been widely used for suppression of high velocity shocks. While linear fluid viscous dampers have been used for a long time, nonlinear fluid viscous dampers show considerable promise due to their superior energy dissipation characteristics and significant reduction in the damper force compared to a linear fluid viscous damper for the same peak displacement. This paper presents results from experimental study to characterize fluid viscous dampers when subjected to half-cycle sine shock excitation. The mathematical formulation and a numerical study to evaluate the relative performance of structures with fluid viscous dampers subjected to short-duration shock (impulse) loading are also discussed. The influence of damper nonlinearity (α) and the supplemental damping ratio (ξ_sd) on response has been investigated. The supplemental damping ratio of nonlinear fluid viscous dampers when subjected to shock excitation is found by equivalent linearization using the concept of equal energy dissipation. The paper also presents some design charts, which can be used for preliminary decisions on parameters of nonlinear dampers to be used in design.     

A Temperature and Salt-Tolerant <Emphasis Type="SmallCaps">l</Emphasis>-Glutaminase from Gangotri Region of Uttarakhand Himalaya: Enzyme Purification and Characterization

Purification and characterization of halotolerant, thermostable alkaline l-glutaminase from a Bacillus sp. LKG-01 (MTCC 10401), isolated from Gangotri region of Uttarakhand Himalaya, is being reported in this paper. Enzyme has been purified 49-fold from cell-free extract with 25% recovery (specific activity 584.2 U/mg protein) by (NH₄)₂SO₄ precipitation followed by anion exchange chromatography and gel filtration. Enzyme has a molecular weight of 66 kDa. l-Glutaminase is most active at pH 11.0 and stable in the pH range 8.0–11.0. Temperature optimum is 70 °C and is completely stable after 3 h pre-incubation at 50 °C. Enzyme reflects more enhanced activity with 1–20% (w/v) NaCl, which is further reduced to 80% when NaCl concentration was increased up to 25%. l-Glutaminase is almost active with K⁺, Zn²⁺, and Ni²⁺ ions and K _m and V _max values of 240 μM and 277.77 ± 1.1 U/mg proteins, respectively. Higher specific activity, purification fold, better halo-tolerance, and thermostability would make this enzyme more attractive for food fermentation with respect to other soil microbe derived l-glutaminase reported so far.     

Determination of the Association Constants of Charge-Transfer Complexes Between N,N-Diethylaniline and Nitro Explosives Using High Performance Thin Layer Chromatography with Scanning Video Densitometry and Spectrophotometry

Charge-transfer (CT) or electron donor-acceptor (EDA) complex formation between organic donors and acceptors has been extensively studied by spectrophotometry and other methods. High performance thin layer chromatography (HPTLC), although extensively used for the identification and quantification of drugs and explosives, has not been used until now to determine the extent of association and the association constants K _DA of charge transfer or EDA complexes between donor (D) and acceptor (A). This paper describes the use of the HPTLC technique with scanning densitometry to identify and determine the association constants K _DA of charge-transfer complexes of N,N-diethylaniline (DEA) with different nitro explosives, namely 1,4-dinitrobenzene (DNB), 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT), in chloroform. Advantages of the HPTLC method are highlighted. The association constants K _DA of the complexes determined using the HPTLC method have been verified and validated spectrophotometrically when the concentrations of D and A are in their stoichiometric ratio. The thermodynamics of the complex formation reaction were obtained spectrophotometrically from measurements of the association constants K _DA at five different temperatures ranging from 293 to 313 K, when D and A are in their stoichiometric ratio and also when A≫D.