Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

3-Phenylisoquinolin-1(2H)-one

The title compound, C15H11NO, consists of a planar isoquinolinone group to which a phenyl ring is attached in a twisted fashion [dihedral angle = 39.44 (4)degrees]. The crystal packing is dominated by intermolecular N-H center dot center dot center dot O and C-H center dot center dot center dot O hydrogen bonds which define centrosymmetric dimeric entitities.

How Good is the Assumption About Visible Surface Reflectance in MODIS Aerosol Retrieval Over Land? A Comparison With Aircraft Measurements Over an Urban Site in India

In this paper, we discuss the measurements of spectral surface reflectance (rho(s)(lambda)) in the wavelength range 350-2500 nm measured using a spectroradiometer onboard a low-flying aircraft over Bangalore (12.95 degrees N, 77.65 degrees E), an urban site in southern India. The large discrepancies in the retrieval of aerosol propertiesover land by the Moderate-Resolution Imaging Spectroradiometer (MODIS), which could be attributed to the inaccurate estimation of surface reflectance at many sites in India and elsewhere, provided motivation for this paper. The aim of this paper was to verify the surface reflectance relationships assumed by the MODIS aerosol algorithm for the estimation of surface reflectance in the visible channels (470 and 660 nm) from the surface reflectance at 2100 nm for aerosol retrieval over land. The variety of surfaces observed in this paper includes green and dry vegetations, bare land, and urban surfaces. The measuredreflectance data were first corrected for the radiative effects of atmosphere lying between the ground and aircraft using the Second Simulation of Satellite Signal in the Solar Spectrum (6S) radiative transfer code. The corrected surface reflectance in the MODIS's blue (rho(s)(470)), red (rho(s)(660)), and shortwave-infrared (SWIR) channel (rho(s)(2100)) was linearly correlated. We found that the slope of reflectance relationship between 660 and 2100 nm derived from the forward scattering data was 0.53 with an intercept of 0.07, whereas the slope for the relationship between the reflectance at 470 and 660 nm was 0.85. These values are much higher than the slope (similar to 0.49) for either wavelengths assumed by the MODIS aerosol algorithm over this region. The reflectance relationship for the backward scattering data has a slope of 0.39, with an intercept of 0.08 for 660 nm, and 0.65, with an intercept of 0.08 for 470 nm. The large values of the intercept (which is very small in the MODIS reflectance relationships) result in larger values of absolute surface reflectance in the visible channels. The discrepancy between the measured and assumed surface reflectances could lead to error in the aerosol retrieval. The reflectance ratio (rho(s)(660)/rho(s)(2100)) showed a clear dependence on the N D V I-SWIR where the ratio increased from 0.5 to 1 with an increase in N V I-SWIR from 0 to 0.5. The high correlation between the reflectance at SWIR wavelengths (2100, 1640, and 1240 nm) indicated an opportunity to derive the surface reflectance and, possibly, aerosol properties at these wavelengths. We need more experiments to characterize the surface reflectance and associated inhomogeneity of land surfaces, which play a critical role in the remote sensing of aerosols over land.

Biochemical and structural characterization of residue 96 mutants of Plasmodium falciparum triosephosphate isomerase: active-site loop conformation, hydration and identification of a dimer-interface ligand-binding site

Plasmodium falciparum TIM (PfTIM) is unique in possessing a Phe residue at position 96 in place of the conserved Ser that is found in TIMs from the majority of other organisms. In order to probe the role of residue 96, three PfTIM mutants, F96S, F96H and F96W, have been biochemically and structurally characterized. The three mutants exhibited reduced catalytic efficiency and a decrease in substrate-binding affinity, with the most pronounced effects being observed for F96S and F96H. The k(cat) values and K-m values are (2.54 +/- 0.19) x 10(5) min(-1) and 0.39 +/- 0.049 mM, respectively, for the wild type; (3.72 +/- 0.28) x 10(3) min(-1) and 2.18 +/- 0.028 mM, respectively, for the F96S mutant;(1.11 +/- 0.03) x 10(4) min(-1) and 2.62 +/- 0.042 mM, respectively, for the F96H mutant; and (1.48 +/- 0.05) x 10(5) min(-1) and 1.20 +/- 0.056 mM, respectively, for the F96W mutant. Unliganded and 3-phosphoglycerate (3PG) complexed structures are reported for the wild-type enzyme and the mutants. The ligand binds to the active sites of the wild-type enzyme (wtPfTIM) and the F96W mutant, with a loop-open state in the former and both open and closed states in the latter. In contrast, no density for the ligand could be detected at the active sites of the F96S and F96H mutants under identical conditions. The decrease in ligand affinity could be a consequence of differences in the water network connecting residue 96 to Ser73 in the vicinity of the active site. Soaking of crystals of wtPfTIM and the F96S and F96H mutants resulted in the binding of 3PG at a dimer-interface site. In addition, loop closure at the liganded active site was observed for wtPfTIM. The dimer-interface site in PfTIM shows strong electrostatic anchoring of the phosphate group involving the Arg98 and Lys112 residues of PfTIM.

The crystal and molecular structure of benzyloxycarbonyl-a-amino-isobutyryl-L-prolyl-methylamide. The observation of an X2-Pro3 Type III b-turn

The crystal and molecular structure of N-benzyloxycarbonyl-a-aminoisobutyryl-L-prolyl methylamide, the amino terminal dipeptide fragment of alamethicin, has been determined using direct methods. The compound crystallizes in the orthorhombic system with the space group P212-21. Cell dimensions are a = 7.705 A, b = 11.365 A, and c = 21.904 A. The structure has been refined using conventional procedures to a final R factor of 0.054. The molecular structure possesses a 4 - 1 intramolecular N-H--0 hydrogen bond formed between the CO group of the urethane moiety and the NH group of the methylamide function. The peptide backbone adopts the type 111 P-turn conformation, with 42 = -51.0°, +* = -39.7",&j = -65.0', $3 = -25.4'. An unusual feature is the occurrence of the proline residue at position 3 of the P-turn. The observed structure supports the view that Aib residues initiate the formation of type 111 @-turn conformations. The pyrrolidine ring is puckered in Cy-exo fashion.

Process variability-aware statistical hybrid modeling of dynamic power dissipation in 65 nm CMOS designs

A generalized technique is proposed for modeling the effects of process variations on dynamic power by directly relating the variations in process parameters to variations in dynamic power of a digital circuit. The dynamic power of a 2-input NAND gate is characterized by mixed-mode simulations, to be used as a library element for 65mn gate length technology. The proposed methodology is demonstrated with a multiplier circuit built using the NAND gate library, by characterizing its dynamic power through Monte Carlo analysis. The statistical technique of Response. Surface Methodology (RSM) using Design of Experiments (DOE) and Least Squares Method (LSM), are employed to generate a "hybrid model" for gate power to account for simultaneous variations in multiple process parameters. We demonstrate that our hybrid model based statistical design approach results in considerable savings in the power budget of low power CMOS designs with an error of less than 1%, with significant reductions in uncertainty by atleast 6X on a normalized basis, against worst case design.

Radiative effects of aerosols at an urban location in southern India: Observations versus model

The radiative impact of aerosols is one of the largest sources of uncertainty in estimating anthropogenic climate perturbations. Here we have used independent ground-based radiometer measurements made simultaneously with comprehensive measurements of aerosol microphysical and optical properties at a highly populated urban site, Bangalore (13.02 degrees N, 77.6 degrees E) in southern India during a dedicated campaign during winter of 2004 and summer and pre-monsoon season of 2005. We have also used longer term measurements carried out at this site to present general features of aerosols over this region. The aerosol radiative impact assessments were made from direct measurements of ground reaching irradiance as well as by incorporating measured aerosol properties into a radiative transfer model. Large discrepancies were observed between measured and modeled (using radiative transfer models, which employed measured aerosol properties) radiative impacts. It appears that the presence of elevated aerosol layers and (or) inappropriate description of aerosol state of mixing are (is) responsible for the discrepancies. On a monthly scale reduction of surface irradiance due to the presence of aerosols (estimated using radiative flux measurements) varies from 30 to 65 W m(-2). The lowest values in surface radiative impact were observed during June when there is large reduction in aerosol as a consequence of monsoon rainfall. Large increase in aerosol-induced surface radiative impact was observed from winter to summer. Our investigations re-iterate the inadequacy of aerosol measurements at the surface alone and importance of representing column properties (using vertical profiles) accurately in order to assess aerosol-induced climate changes accurately. (C) 2010 Elsevier Ltd. All rights reserved.

Reactions of copper(I) aryloxides with phenyl isothiocyanate: steric and ligand control in the oligomerization of [N-phenylimino(aryloxy)methanethiolato]copper(I) complexes

The preparation of five different copper(I) complexes [CuSC(=NPh)(OAr)}L(n)]m (1-5) formed by the insertion of PhNCS into the Cu-OAr bond and the crystal structure analyses of three of them have been carried out. A monomeric species 1 (OAr = 2,6-dimethylphenoxide) is formed in the presence of excess PPh3 (n = 2, m = 1) and crystallizes as triclinic crystals with a = 12.419(4) angstrom, b = 13.298(7) angstrom, c = 15.936(3) angstrom, alpha = 67.09(3)-degrees, beta = 81.63(2)-degrees, gamma = 66.54(3)-degrees, V = 2224(2) angstrom3, and Z = 2. The structure was refined by the least-squares method to final R and R(w) values of 0.038 and 0.044, respectively, for 7186 unique reflections. Copper(I) 2,5-di-tert-butyl-4-methylphenoxide results in the formation of a dimeric species 2 in the presence of P(OMe)3 (n = 1, m = 2), where the coordination around Cu is trigonal. Crystals of 2 were found to be orthorhombic with a = 15.691(2) angstrom, b = 18.216(3) angstrom, c = 39.198(5) angstrom, v = 11204(3) angstrom3, and Z = 8. Least-squares refinement gave final residuals of R = 0.05 and R(w) = 0.057 with 6866 unique reflections. A tetrameric species 3 results when PPh3 is replaced by P(OMe)3 in the coordination sphere of copper(I) 2,6-dimethylphenoxide. It crystallizes in the space group P1BAR with a = 11.681 (1) angstrom, b = 13.373(2) angstrom, c = 20.127(1) angstrom, a = 88.55(l)-degrees, beta = 89.65(l)-degrees, gamma = 69.28(1)-degrees, V = 2940(l) angstrom3, and Z = 2. Least-squares refinement of the structure gave final values of 0.043 and 0.05 for R and R(w) respectively using 12214 unique reflections. In addition, a dimeric species 4 is formed when 1 equiv of PPh3 is added to the copper(I) 4-methylphenoxide, while with an excess of PPh3 a monomeric species 5 is isolated. Some interconversions among these complexes are also reported.

Studies of interfaces in Al-65 Cu20Fe15

The study of interfaces in quasicrystalline alloys is relatively new. Apart From the change in orientation, symmetry and chemistry which can occur across homophase and heterophase boundaries in crystalline materials, we have the additional, exciting possibility of an interface between quasicrystalline and its rational approximant. High resolution electron microscopy is a powerful technique to study the structural details of such interfaces. We report the results of a HREM study of the interface between the icosahedral phase and the related Al13Fe4 type monoclinic phase in melt spun and annealed Al65Cu20Fe15 alloy.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.

Reducing Buffer Requirements in Core Routers using Dynamic Buffering

Earlier studies have exploited statistical multiplexing of flows in the core of the Internet to reduce the buffer requirement in routers. Reducing the memory requirement of routers is important as it enables an improvement in performance and at the same time a decrease in the cost. In this paper, we observe that the links in the core of the Internet are typically over-provisioned and this can be exploited to reduce the buffering requirement in routers. The small on-chip memory of a network processor (NP) can be effectively used to buffer packets during most regimes of traffic. We propose a dynamic buffering strategy which buffers packets in the receive and transmit buffers of a NP when the memory requirement is low. When the buffer requirement increases due to bursts in the traffic, memory is allocated to packets in the off-chip DRAM. This scheme effectively mitigates the DRAM access bottleneck, as only a part of the traffic is stored in the DRAM. We build a Petri net model and evaluate the proposed scheme with core Internet like traffic. At 77% link utilization, the dynamic buffering scheme has a drop rate of just 0.65%, whereas the traditional DRAM buffering has 4.64% packet drop rate. Even with a high link utilization of 90%, which rarely happens in the core, our dynamic buffering results in a packet drop rate of only 2.17%, while supporting a throughput of 7.39 Gbps. We study the proposed scheme under different conditions to understand the provisioning of processing threads and to determine the queue length at which packets must be buffered in the DRAM. We show that the proposed dynamic buffering strategy drastically reduces the buffering requirement while still maintaining low packet drop rates.

Analog/RF Built-in-Self-Test Subsystem for a Mobile Broadcast Video Receiver in 65-nm CMOS

A built-in-self-test (BIST) subsystem embedded in a 65-nm mobile broadcast video receiver is described. The subsystem is designed to perform analog and RF measurements at multiple internal nodes of the receiver. It uses a distributed network of CMOS sensors and a low bandwidth, 12-bit A/D converter to perform the measurements with a serial bus interface enabling a digital transfer of measured data to automatic test equipment (ATE). A perturbation/correlation based BIST method is described, which makes pass/fail determination on parts, resulting in significant test time and cost reduction.

Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta): New water gas shift (WGS) catalysts

Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) and Ce(0.67)Fe(0.33)O(2-delta) have been synthesized by a new low temperature sonochemical method using diethylenetriamine as a complexing agent. Due to the substitution of Fe and Pt ions in CeO(2), lattice oxygen is activated in Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). Hydrogen uptake studies show strong reduction peaks at 125 C in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) against a hydrogen uptake peak at 420 degrees C in Ce(0.67)Fe(0.33)O(2-delta). Fe substituted ceria, Ce(0.67)Fe(0.33)O(2-delta) itself acts as a catalyst for CO oxidation and water gas shift (WGS) reactions at moderate temperatures. The rate of CO conversion in WGS with Pt free Ce(0.65)Fe(0.33)O(2-delta) is 2.8 mu mol g(-1) s(-1) at 450 C and with Pt substituted Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) is 4.05 mu mol g(-1) s(-1) at 275 degrees C. Due to the synergistic interaction of the Pt ion with Ce and Fe ions in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta), the catalyst showed much higher activity for CO oxidation and WGS reactions compared to Ce(0.67)Fe(0.33)O(2-delta). A reverse WGS reaction does not occur over Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). The catalyst also does not deactivate even when operated for a long time. Nearly 100% conversion of CO to CO(2) with 100% H(2) selectivity is observed in WGS reactions even up to 550 degrees C. (C) 2011 Elsevier B.V. All rights reserved.

Model projections for household energy use in India

Energy use in developing countries is heterogeneous across households. Present day global energy models are mostly too aggregate to account for this heterogeneity. Here, a bottom-up model for residential energy use that starts from key dynamic concepts on energy use in developing countries is presented and applied to India. Energy use and fuel choice is determined for five end-use functions (cooking, water heating, space heating, lighting and appliances) and for five different income quintiles in rural and urban areas. The paper specifically explores the consequences of different assumptions for income distribution and rural electrification on residential sector energy use and CO(2) emissions, finding that results are clearly sensitive to variations in these parameters. As a result of population and economic growth, total Indian residential energy use is expected to increase by around 65-75% in 2050 compared to 2005, but residential carbon emissions may increase by up to 9-10 times the 2005 level. While a more equal income distribution and rural electrification enhance the transition to commercial fuels and reduce poverty, there is a trade-off in terms of higher CO(2) emissions via increased electricity use. (C) 2011 Elsevier Ltd. All rights reserved.