RES-TOCSY: a simple approach to resolve overlapped H-1 NMR spectra of enantiomers

Chiral auxiliaries are used for the NMR spectroscopic study of enantiomers. Often the presence of impurities, overlap of peaks, line broadening and the multiplicity pattern restrict the chiral analysis in the 1D H-1 NMR spectrum. The present study introduces a simple 2D H-1 NMR experiment to unravel the overlapped spectrum. The experiment separates the spectra of enantiomers, thereby allowing the unambiguous assignment of all the coupled peaks and the measurement of enantiomeric excess (ee) from a single experiment even in combinatorial mixtures.

Optical bio-sensing devices based on etched fiber Bragg gratings coated with carbon nanotubes and graphene oxide along with a specific dendrimer

We demonstrate that etched fiber Bragg gratings (eFBGs) coated with single walled carbon nanotubes (SWNTs) and graphene oxide (GO) are highly sensitive and accurate biochemical sensors. Here, for detecting protein concanavalin A (Con A), mannose-functionalized poly(propyl ether imine) (PETIM) dendrimers (DMs) have been attached to the SWNTs (or GO) coated on the surface modified eFBG. The dendrimers act as multivalent ligands, having specificity to detect lectin Con A. The specificity of the sensor is shown by a much weaker response (factor of similar to 2500 for the SWNT and similar to 2000 for the GO coated eFBG) to detect non specific lectin peanut agglutinin. DM molecules functionalized GO coated eFBG sensors showed excellent specificity to Con A even in the presence of excess amount of an interfering protein bovine serum albumin. The shift in the Bragg wavelength (Delta lambda(B)) with respect to the lambda(B) values of SWNT (or GO)-DM coated eFBG for various concentrations of lectin follows Langmuir type adsorption isotherm, giving an affinity constant of similar to 4 x 10(7) M-1 for SWNTs coated eFBG and similar to 3 x 10(8) M-1 for the GO coated eFBG. (C) 2014 Elsevier B.V. All rights reserved.

Elastic Resources Framework in IaaS, preserving performance SLAs

Elasticity in cloud systems provides the flexibility to acquire and relinquish computing resources on demand. However, in current virtualized systems resource allocation is mostly static. Resources are allocated during VM instantiation and any change in workload leading to significant increase or decrease in resources is handled by VM migration. Hence, cloud users tend to characterize their workloads at a coarse grained level which potentially leads to under-utilized VM resources or under performing application. A more flexible and adaptive resource allocation mechanism would benefit variable workloads, such as those characterized by web servers. In this paper, we present an elastic resources framework for IaaS cloud layer that addresses this need. The framework provisions for application workload forecasting engine, that predicts at run-time the expected demand, which is input to the resource manager to modulate resource allocation based on the predicted demand. Based on the prediction errors, resources can be over-allocated or under-allocated as compared to the actual demand made by the application. Over-allocation leads to unused resources and under allocation could cause under performance. To strike a good trade-off between over-allocation and under-performance we derive an excess cost model. In this model excess resources allocated are captured as over-allocation cost and under-allocation is captured as a penalty cost for violating application service level agreement (SLA). Confidence interval for predicted workload is used to minimize this excess cost with minimal effect on SLA violations. An example case-study for an academic institute web server workload is presented. Using the confidence interval to minimize excess cost, we achieve significant reduction in resource allocation requirement while restricting application SLA violations to below 2-3%.

An in situ carbon-grafted alkaline iron electrode for iron-based accumulators

An in situ carbon-grafted alkaline iron electrode prepared from the active material obtained by decomposing the alpha-FeC2O4 center dot 2H(2)O-polyvinyl alcohol (PVA) composite at 600 degrees C in a vacuum is reported. The active material comprises a mixture of a-Fe and Fe3O4 with the former as the prominent component. A specific discharge capacity in excess of 400 mA h g(-1) at a current density of 100 mA g(-1) is obtained with a faradaic efficiency of 80% for the iron electrode made from carbon-grafted active material (CGAM). The enhanced performance of the alkaline iron electrode is attributed to the increased amount of metallic iron in the active material and its concomitant in situ carbon grafting.

Structural and thermodynamic properties of Fe1.12Te with multiple phase transitions

The parent compound of iron chalcogenide superconductors, Fe1+yTe, with a range of excess Fe concentrations exhibits intriguing structural and magnetic properties. Here, the interplay of magnetic and structural properties of Fe1.12Te single crystals have been probed by low-temperature synchrotron X-ray powder diffraction, magnetization, and specific heat measurements. Thermodynamic measurements reveal two distinct phase transitions, considered unique to samples possessing excess Fe content in the range of 0.11 <= y <= 0.13. On cooling, an antiferromagnetic transition, T-N approximate to 57K is observed. A closer examination of powder diffraction data suggests that the transition at TN is not purely magnetic, but accompanied by the commencement of a structural phase transition from tetragonal to orthorhombic symmetry. This is followed by a second prominent first-order structural transition at T-S with T-S < T-N, where an onset of monoclinic distortion is observed. The results point to a strong magneto-structural coupling in this material. (C) 2014 AIP Publishing LLC.

Exclusive ring opening of gem-dihalo-1,2-cyclopropanated oxyglycal to oxepines in AgOAc

Treatment of gem-dihalo-1,2-cyclopropanated D-oxyglycal with primary, secondary, and unsaturated alcohols, in the presence of AgOAc, leads to the formation of chloro-oxepines exclusively. Reaction of the resulting 2-chloro-oxepines with excess alcohol in the presence of AgOAc, do not promote further reactions. This result is in contrast to the reactions of D-glucal derived halo-oxepine with alcohols known previously that lead to the formation of furanoses as the major product under similar reaction conditions. Observation of this study consolidates the reactivity differences of gem-dihalo-1,2-cyclopropanated oxyglycals, as compared to gem-dihalo- 1,2-cyclopropanated glycals. (C) 2014 Elsevier Ltd. All rights reserved.

Design and analysis of integrated optic quadrature phase shift keying modulator

Quadrature phase shift keying (QPSK) is one of the most popular modulation schemes in coherent optical communication systems for data rates in excess of 40 Gbps because of its high spectral efficiency. This paper proposes a simple method of implementing a QPSK modulator in integrated optic (IO) domain. The QPSK modulator is realized using standard IO components, such as Y-branches and electro-optic modulators (EOMs). Design optimization of EOM is carried out considering the fabrication constraints, miniaturization aspects, and simplicity. Also, the interdependency between electrode length, operating voltage, and electrode gap of an EOM has been captured in the form of a family of curves. These plots enable designing of EOMs for custom requirements. An innovative approach has been adopted in demonstrating the operation of IO QPSK modulator in terms of phase data extracted from beam propagation model. The results obtained by this approach have been verified using the conventional interferometric approach. The operation of the proposed IO QPSK modulator is experimentally demonstrated. The design of IO QPSK modulator is taken up as a part of a broader scheme that aims at generation of QPSK modulated microwave signal based on optical heterodyning. (C) 2014 Society of Photo-Optical Instrumentation Engineers (SPIE)

SELECTIVE ALDEHYDE REDUCTION IN KETOALDEHYDES WITH NaBH4-Na2CO3-H2O AT ROOM TEMPERATURES

A variety of aliphatic and aromatic ketoaldehydes were reduced to the corresponding ketoalcohols with a mixture of sodium borohydride (1.2 equivalents) and sodium carbonate (sixfold molar excess) in water. Reactions were performed at room temperatures over (typically) 2 h, and yields of isolated products generally ranged from 70% to 85%. A biscarbonate-borane complex, (BH3)(2)CO2](2-) 2Na(+), possibly formed from the reagent mixture, is likely the active reductant. The moderated reactivity of this acylborane species would explain the chemoselectivity observed in the reactions. The readily available reagents and the mild aqueous conditions make for ease of operation and environmental compatibility, and make a useful addition to available methodology.

Orbital phase resolved spectroscopy of GX 301-2 with MAXI

GX 301-2, a bright high-mass X-ray binary with an orbital period of 41.5 d, exhibits stable periodic orbital intensity modulations with a strong pre-periastron X-ray flare. Several models have been proposed to explain the accretion at different orbital phases, invoking accretion via stellar wind, equatorial disc, and accretion stream from the companion star. We present results from exhaustive orbital phase resolved spectroscopic measurements of GX 301-2 using data from the Gas Slit Camera onboard MAXI. Using spectroscopic analysis of the MAXI data with unprecedented orbital coverage for many orbits continuously, we have found a strong orbital dependence of the absorption column density and equivalent width of the iron emission line. A very large equivalent width of the iron line along with a small value of the column density in the orbital phase range 0.10-0.30 after the periastron passage indicates the presence of high density absorbing matter behind the neutron star in this orbital phase range. A low energy excess is also found in the spectrum at orbital phases around the pre-periastron X-ray flare. The orbital dependence of these parameters are then used to examine the various models about mode of accretion on to the neutron star in GX 301-2.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Impacts of modern transitions on thermal comfort in vernacular dwellings in warm-humid climate of Sugganahalli (India)

Sugganahalli, a rural vernacular community in a warm-humid region in South India, is under transition towards adopting modern construction practices. Vernacular local building elements like rubble walls and mud roofs are given way to burnt brick walls and reinforced cement concrete (RCC)/tin roofs. Over 60% of Indian population is rural, and implications of such transitions on thermal comfort and energy in buildings are crucial to understand. Vernacular architecture evolves adopting local resources in response to the local climate adopting passive solar designs. This paper investigates the effectiveness of passive solar elements on the indoor thermal comfort by adopting modern climate-responsive design strategies. Dynamic simulation models validated by measured data have also been adopted to determine the impact of the transition from vernacular to modern material-configurations. Age-old traditional design considerations were found to concur with modern understanding into bio-climatic response and climate-responsiveness. Modern transitions were found to increase the average indoor temperatures in excess of 7 degrees C. Such transformations tend to shift the indoor conditions to a psychrometric zone that is likely to require active air-conditioning. Also, the surveyed thermal sensation votes were found to lie outside the extended thermal comfort boundary for hot developing countries provided by Givoni in the bio-climatic chart.

A versatile ternary ionic complex for chiral discrimination of molecules with diverse functionalities using H-1 NMR

This study reports a simple, efficient and versatile protocol developed for NMR spectroscopic enantiodiscrimination of molecules containing diverse functional -groups, such as amino alcohols, secondary alcohols, cyanohydrins, oxazolidones, diols, thiones and epoxides, using a phosphorous based three component mixture. The simple mixing and shaking of enantiopure 1,1'-binaphthyt-2,2'-diyl hydrogenphosphate (BNPA), 4-(dimethylamino)pyridine (DMAP) and a chiral analyte in the solvent CDCl3 served as a chiral solvating agent and resulted in well dispersed peaks for each enantiomer in the H-1 NMR spectrum. Discrimination could be achieved not only for the proton at the chiral centre, but also for multiple proton sites. The devised approach also permitted the precise measurement of the enantiomeric excess (ee).

Cooling a Band Insulator with a Metal: Fermionic Superfluid in a Dimerized Holographic Lattice

A cold atomic realization of a quantum correlated state of many fermions on a lattice, eg. superfluid, has eluded experimental realization due to the entropy problem. Here we propose a route to realize such a state using holographic lattice and confining potentials. The potentials are designed to produces aband insulating state (low heat capacity) at the trap center, and a metallic state (high heat capacity) at the periphery. The metal ``cools'' the central band insulator by extracting out the excess entropy. The central band insulator can be turned into a superfluid by tuning an attractive interaction between the fermions. Crucially, the holographic lattice allows the emergent superfluid to have a high transition temperature - even twice that of the effective trap temperature. The scheme provides a promising route to a laboratory realization of a fermionic lattice superfluid, even while being adaptable to simulate other many body states.

CINCINNATA in Antirrhinum majus directly modulates genes involved in cytokinin and auxin signaling

Mutations in the CINCINNATA (CIN) gene in Antirrhinum majus and its orthologs in Arabidopsis result in crinkly leaves as a result of excess growth towards the leaf margin. CIN homologs code for TCP (TEOSINTE-BRANCHED 1, CYCLOIDEA, PROLIFERATING CELL FACTOR 1 AND 2) transcription factors and are expressed in a broad zone in a growing leaf distal to the proliferation zone where they accelerate cell maturation. Although a few TCP targets are known, the functional basis of CIN-mediated leaf morphogenesis remains unclear. We compared the global transcription profiles of wild-type and the cin mutant of A. majus to identify the targets of CIN. We cloned and studied the direct targets using RNA in situ hybridization, DNA-protein interaction, chromatin immunoprecipitation and reporter gene analysis. Many of the genes involved in the auxin and cytokinin signaling pathways showed altered expression in the cin mutant. Further, we showed that CIN binds to genomic regions and directly promotes the transcription of a cytokinin receptor homolog HISTIDINE KINASE 4 (AmHK4) and an IAA3/SHY2 (INDOLE-3-ACETIC ACID INDUCIBLE 3/SHORT HYPOCOTYL 2) homolog in A. majus. Our results suggest that CIN limits excess cell proliferation and maintains the flatness of the leaf surface by directly modulating the hormone pathways involved in patterning cell proliferation and differentiation during leaf growth. 10.1111/(ISSN)1469-8137

Amorphous W-S-N thin films: The atomic structure behind ultra-low friction

Amorphous W-S-N in the form of thin films has been identified experimentally as an ultra-low friction material, enabling easy sliding by the formation of a WS2 tribofilm. However, the atomic-level structure and bonding arrangements in amorphous W-S-N, which give such optimum conditions for WS2 formation and ultra-low friction, are not known. In this study, amorphous thin films with up to 37 at.% N are deposited, and experimental as well as state-of-the-art ab initio techniques are employed to reveal the complex structure of W-S-N at the atomic level. Excellent agreement between experimental and calculated coordination numbers and bond distances is demonstrated. Furthermore, the simulated structures are found to contain N bonded in molecular form, i.e. N-2, which is experimentally confirmed by near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy analysis. Such N-2 units are located in cages in the material, where they are coordinated mainly by S atoms. Thus this ultra-low friction material is shown to be a complex amorphous network of W, S and N atoms, with easy access to W and S for continuous formation of WS2 in the contact region, and with the possibility of swift removal of excess nitrogen present as N-2 molecules. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.