The substrate dependent competitive formation of cyclobutanones and cyclopentanones in an intramolecular rhodium carbenoid CH insertion reaction: enantiospecific total synthesis of silphiperfol-6-ene

The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the gamma- and beta-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described. (C) 2012 Elsevier Ltd. All rights reserved.

Low cost calibrated mechanical noisemaker for hearing screening of neonates in resource constrained settings

Background & objectives: There is a need to develop an affordable and reliable tool for hearing screening of neonates in resource constrained, medically underserved areas of developing nations. This study valuates a strategy of health worker based screening of neonates using a low cost mechanical calibrated noisemaker followed up with parental monitoring of age appropriate auditory milestones for detecting severe-profound hearing impairment in infants by 6 months of age. Methods: A trained health worker under the supervision of a qualified audiologist screened 425 neonates of whom 20 had confirmed severe-profound hearing impairment. Mechanical calibrated noisemakers of 50, 60, 70 and 80 dB (A) were used to elicit the behavioural responses. The parents of screened neonates were instructed to monitor the normal language and auditory milestones till 6 months of age. This strategy was validated against the reference standard consisting of a battery of tests - namely, auditory brain stem response (ABR), otoacoustic emissions (OAE) and behavioural assessment at 2 years of age. Bayesian prevalence weighted measures of screening were calculated. Results: The sensitivity and specificity was high with least false positive referrals for. 70 and 80 dB (A) noisemakers. All the noisemakers had 100 per cent negative predictive value. 70 and 80 dB (A) noisemakers had high positive likelihood ratios of 19 and 34, respectively. The probability differences for pre- and post- test positive was 43 and 58 for 70 and 80 dB (A) noisemakers, respectively. Interpretation & conclusions: In a controlled setting, health workers with primary education can be trained to use a mechanical calibrated noisemaker made of locally available material to reliably screen for severe-profound hearing loss in neonates. The monitoring of auditory responses could be done by informed parents. Multi-centre field trials of this strategy need to be carried out to examine the feasibility of community health care workers using it in resource constrained settings of developing nations to implement an effective national neonatal hearing screening programme.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

Dual functional performance of fiber Bragg gratings coated with metals using flash evaporation technique

Metallic and other type of coatings on fiber Bragg grating (FBG) sensors alter their sensitivity with thermal and mechanical stress while protecting the fragile optical fiber in harsh sensing surroundings. The behavior of the coated materials is unique in their response to thermal and mechanical stress depending on the thickness and the mode of coating. The thermal stress during the coating affects the temperature sensitivity of FBG sensors. We have explored the thermal response of FBGs coated with Al and Pb to an average thickness of 80 nm using flash evaporation technique where the FBG sensor is mounted in a region at room temperature in an evacuated chamber having a pressure of 10(6) Torr which will minimize any thermal stress during the coating process. The coating thickness is chosen in the nanometer region with the aim to study thermal behavior of nanocoatings and their effect on FBG sensitivity. The sensitivity of FBGs is evaluated from the wavelengths recorded using an optical sensing interrogator sm 130 (Micron Optics) from room temperature to 300 degrees C both during heating and cooling. It is observed that the sensitivity of the metal coated fibers is better than the reference FBG with no coating for the entire range of temperature. For a coating thickness of 80 nm, Al coated FBG is more sensitive than the one coated with Pb up to 170 degrees C and it reverses at higher temperatures. This point is identified as a reversible phase transition in Pb monolayers as the 2-dimensional aspects of the metal layers are dominant in the nanocoatings of Pb. On cooling, the phase transition reverses and the FBGs return to the original state and for repeated cycles of heating and cooling the same pattern is observed. Thus the FBG functions as a sensor of the phase transitions of the coatings also. (C) 2012 Elsevier Inc. All rights reserved.

Evidence of nanoscale structural phase separation in large bandwidth La0.2Sr0.8MnO3

We have investigated the structural evolution of La0.2Sr0.8MnO3 using temperature dependent high resolution synchrotron x-ray diffraction technique. In a wide temperature range, La0.2Sr0.8MnO3 reveals nanoscale structural inhomogeneity consisting of cubic and tetragonal phases. The present results suggest that domains of nanometer size of the tetragonal (low temperature) phase start nucleating in the cubic (high temperature) phase even above the Neel temperature (T-N). The tetragonal phase fraction increases substantially below T-N. Detailed analysis suggests that the twinned phase is tetragonal, orbital ordered, and insulating. At temperatures below 170 K, a small amount of the cubic phase is retained. The present results reveal the significance of the connectivity between the nanoscale structural phase separation with the physical properties.

Texture and microstructure evolution during cold rolling of Cu-Fe laminates prepared by accumulative roll bonding

Multi-layered materials have been made from Cu-Fe with approximately equal volume fractions using the Accumulated Roll Bonding (ARB) technique with less than 1 μm thickness of the individual layers. The so-obtained multi-layers have been subjected to deformation by cold rolling to 25, 50, 75, 87 and 93% reduction in thickness. A detailed characterization has been carried out using X-ray diffraction (line profile analysis and texture measurement) and electron (scanning and transmission) microscopy. It has been found that Fe layers are disintegrated whereas Cu retains its continuity within a layer. Microstructural Characterization from X-Ray Line profile Analysis (XRDLPA) through Variance Method reveals that large amount of strain is initially carried by Cu layers during deformation. In the Cu-Fe layer, the texture is comparatively weaker in Cu layer and strong in Fe layers. Brass Component increases up to 75% reduction and then decreases, while the ratio of Cu/S and Bs/S remains almost constant through out the deformation. After 50% reduction, dynamic recovery is predominant as indicated by the increase in the amount of low angle grain boundaries and decrease in dislocation density. The presence of R component indicates continuous dynamic recovery and recrystallization (CDRR) at the advanced stage of deformation.

Acoustic and optical phonon dynamics from femtosecond time-resolved optical spectroscopy of the superconducting iron pnictide Ca(Fe0.944Co0.056)(2)As-2

We report the temperature evolution of coherently excited acoustic and optical phonon dynamics in the superconducting iron pnictide single crystal Ca(Fe0.944Co0.056)(2)As-2 across the spin density wave transition at T-SDW similar to 85 K and the superconducting transition at T-SC similar to 20 K. The strain pulse propagation model applied to the generation of the acoustic phonons yields the temperature dependence of the optical constants, and longitudinal and transverse sound velocities in the temperature range from 3.1 K to 300 K. The frequency and dephasing times of the phonons show anomalous temperature dependence below T-SC indicating a coupling of these low-energy excitations with the Cooper-pair quasiparticles. A maximum in the amplitude of the acoustic modes at T similar to 170 is seen, attributed to spin fluctuations and strong spin-lattice coupling before T-SDW. Copyright (c) EPLA, 2012

Physically Based, Hydrologic Model Results Based on Three Precipitation Products

The main objective of the study is to examine the accuracy of and differences among simulated streamflows driven by rainfall estimates from a network of 22 rain gauges spread over a 2,170 km2 watershed, NEXRAD Stage III radar data, and Tropical Rainfall Measuring Mission (TRMM) 3B42 satellite data. The Gridded Surface Subsurface Hydrologic Analysis (GSSHA), a physically based, distributed parameter, grid-structured, hydrologic model, was used to simulate the June-2002 flooding event in the Upper Guadalupe River watershed in south central Texas. There were significant differences between the rainfall fields estimated by the three types of measurement technologies. These differences resulted in even larger differences in the simulated hydrologic response of the watershed. In general, simulations driven by radar rainfall yielded better results than those driven by satellite or rain-gauge estimates. This study also presents an overview of effects of land cover changes on runoff and stream discharge. The results demonstrate that, for major rainfall events similar to the 2002 event, the effect of urbanization on the watershed in the past two decades would not have made any significant effect on the hydrologic response. The effect of urbanization on the hydrologic response increases as the size of the rainfall event decreases.

Effect of substrate surface roughness on electric current induced flow of liquid metals

Electric current can induce long-range flow of liquid metals over a conducting substrate. This work reports on the effect of the substrate surface roughness on the liquid metal-front velocity during such a flow. Experiments were conducted by passing electric current through liquid gallium placed over similar to 170 nm thick, 500 mu m wide gold and platinum films of varying roughness. The ensuing flow, thus, resembles micro-fluidics behavior in an open-channel. The liquid-front velocity decreased linearly with the substrate surface roughness; this is attributed to the reduction in the effective electric field along the liquid metal-substrate interface with the substrate surface roughness. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790182]

Loss ratio of the EDF scheduling policy with early discarding technique

This paper considers a firm real-time M/M/1 system, where jobs have stochastic deadlines till the end of service. A method for approximately specifying the loss ratio of the earliest-deadline-first scheduling policy along with exit control through the early discarding technique is presented. This approximation uses the arrival rate and the mean relative deadline, normalized with respect to the mean service time, for exponential and uniform distributions of relative deadlines. Simulations show that the maximum approximation error is less than 4% and 2% for the two distributions, respectively, for a wide range of arrival rates and mean relative deadlines. (C) 2013 Elsevier B.V. All rights reserved.

Seismic site classification and correlation between standard penetration test N value and shear wave velocity for Lucknow city in Indo-Gangetic basin

Subsurface lithology and seismic site classification of Lucknow urban center located in the central part of the Indo-Gangetic Basin (IGB) are presented based on detailed shallow subsurface investigations and borehole analysis. These are done by carrying out 47 seismic surface wave tests using multichannel analysis of surface waves (MASW) and 23 boreholes drilled up to 30 m with standard penetration test (SPT) N values. Subsurface lithology profiles drawn from the drilled boreholes show low- to medium-compressibility clay and silty to poorly graded sand available till depth of 30 m. In addition, deeper boreholes (depth >150 m) were collected from the Lucknow Jal Nigam (Water Corporation), Government of Uttar Pradesh to understand deeper subsoil stratification. Deeper boreholes in this paper refer to those with depth over 150 m. These reports show the presence of clay mix with sand and Kankar at some locations till a depth of 150 m, followed by layers of sand, clay, and Kankar up to 400 m. Based on the available details, shallow and deeper cross-sections through Lucknow are presented. Shear wave velocity (SWV) and N-SPT values were measured for the study area using MASW and SPT testing. Measured SWV and N-SPT values for the same locations were found to be comparable. These values were used to estimate 30 m average values of N-SPT (N-30) and SWV (V-s(30)) for seismic site classification of the study area as per the National Earthquake Hazards Reduction Program (NEHRP) soil classification system. Based on the NEHRP classification, the entire study area is classified into site class C and D based on V-s(30) and site class D and E based on N-30. The issue of larger amplification during future seismic events is highlighted for a major part of the study area which comes under site class D and E. Also, the mismatch of site classes based on N-30 and V-s(30) raises the question of the suitability of the NEHRP classification system for the study region. Further, 17 sets of SPT and SWV data are used to develop a correlation between N-SPT and SWV. This represents a first attempt of seismic site classification and correlation between N-SPT and SWV in the Indo-Gangetic Basin.

Mesostructured-aluminosilicate-Nafion hybrid membranes for direct methanol fuel cells

Organic-inorganic hybrid membranes are prepared from Nafion and acid functionalized aluminosilicate with varying structures and surface areas. Acid-functionalized mesostructured aluminosilicate with cellular foam framework (Al-MSU-F type) of surface area 463 m(2) g(-1), acid-functionalized aluminosilicate molecular sieves (Al-HMS type) of surface area 651 m(2) g(-1) and acid-functionalized mesostructured aluminosilicate with hexagonal network (Al-MCM-41 type) of surface area 799 m(2) g(-1) have been employed as potential filler materials to form hybrid membranes with Nafion. The structural behavior, water uptake, ion-exchange capacity, proton conductivity and methanol permeability of the hybrid membranes are extensively investigated. Direct methanol fuel cells (DMFCs) with Al-HMS-Nafion and Al-MCM-41-Nafion hybrid membranes deliver respective peak power-densities of 170 mW cm(-2) and 246 mW cm(-2), while a peak power-density of only 48 mW cm(-2) is obtained for the DMFC employing pristine recast-Nafion membrane under identical operating conditions. The unique properties associated with hybrid membranes could be exclusively attributed to the presence of pendant sulfonic-acid groups in the filler materials, which provide proton-conducting pathways between the filler and matrix in the hybrid membranes, and facilitate proton transport with adequate balance between proton conductivity and methanol permeability. (C) 2012 Elsevier Ltd. All rights reserved.

Some questions on integral geometry on noncompact symmetric spaces of higher rank

Let be a noncompact symmetric space of higher rank. We consider two types of averages of functions: one, over level sets of the heat kernel on and the other, over geodesic spheres. We prove injectivity results for functions in which extend the results in Pati and Sitaram (Sankya Ser A 62:419-424, 2000).

A soluble-lead redox flow battery with corrugated graphite sheet and reticulated vitreous carbon as positive and negative current collectors

A soluble-lead redox flow battery with corrugated-graphite sheet and reticulated-vitreous carbon as positive and negative current collectors is assembled and performance tested. In the cell, electrolyte comprising of 1 center dot 5 M lead (II) methanesulfonate and 0 center dot 9 M methanesulfonic acid with sodium salt of lignosulfonic acid as additive is circulated through the reaction chamber at a flow rate of 50 ml min (-aEuro parts per thousand 1). During the charge cycle, pure lead (Pb) and lead dioxide (PbO2) from the soluble lead (II) species are electrodeposited onto the surface of the negative and positive current collectors, respectively. Both the electrodeposited materials are characterized by XRD, XPS and SEM. Phase purity of synthesized lead (II) methanesulfonate is unequivocally established by single crystal X-ray diffraction followed by profile refinements using high resolution powder data. During the discharge cycle, electrodeposited Pb and PbO2 are dissolved back into the electrolyte. Since lead ions are produced during oxidation and reduction at the negative and positive plates, respectively there is no risk of crossover during discharge cycle, preventing the possibility of lowering the overall efficiency of the cell. As the cell employs a common electrolyte, the need of employing a membrane is averted. It has been possible to achieve a capacity value of 114 mAh g (-aEuro parts per thousand 1) at a load current-density of 20 mA cm (-aEuro parts per thousand 2) with the cell at a faradaic efficiency of 95%. The cell is tested for 200 cycles with little loss in its capacity and efficiency.