Syntheses and structural investigation of some alkali metal ion-mediated (LVO2-)-O-V (L2- = tridentate ONO ligands) species: DNA binding, photoinduced DNA cleavage and cytotoxic activities

Eight alkali metal ion-mediated dioxidovanadium(V), {(VO2L1-6)-O-V} A(H2O)n]proportional to, complexes for A = Li+, Na+, K+ and Cs+, containing tridentate aroylhydrazonate ligands coordinating via ONO donor atoms, are described. All the synthesised ligands and the metal complexes were successfully characterised by elemental analysis, IR, UV-Vis and NMR spectroscopy. X-ray crystallographic investigation of 3, 5-7 shows the presence of distorted NO4 coordination geometries for LVO2- in each case, and varying mu-oxido and/ or mu-aqua bridging with interesting variations correlated with the size of the alkali metal ions: with small Li+, no bridging-O is found but four ion aggregates are found with Na+, chains for K+ and finally, layers for Cs+. Two (5) or three-dimensional (3, 6 and 7) architectures are consolidated by hydrogen bonding. The dioxidovanadium(V) complexes were found to exhibit DNA binding activity due to their interaction with CT-DNA by the groove binding mode, with binding constants ranging from 10(3) to 10(4) M-1. Complexes 1-8 were also tested for DNA nuclease activity against pUC19 plasmid DNA which showed that 6 and 7 had the best DNA binding and photonuclease activity; these results support their good protein binding and cleavage activity with binding constants ranging from 104 to 105 M-1. Finally, the in vitro antiproliferative activity of all complexes was assayed against the HeLa cell line. Some of the complexes (2, 5, 6 and 7) show considerable activity compared to commonly used chemotherapeutic drugs. The variation in cytotoxicity of the complexes is influenced by the various functional groups attached to the aroylhydrazone derivative.

12 V / kilo-Farad Range Lead-Carbon Hybrid Ultracapacitors and Their Envisaged Applications

12 V / kilo-Farad (kF) range substrate-integrated lead-carbon hybrid ultracapacitors (HUCs) wherein the conventional positive plates of lead-acid batteries are replaced with substrate-integrated PbO2 positive plates and the negative plates are replaced with carbon-coated graphitic electrodes, providing totally non-faradaic and corrosion-free electrodes, are developed and performance tested. Constant-current discharge data at varying load-currents, constant-power discharge data at varying power values, and the capacitance data at different temperature for a 12 V / kF range substrate-integrated lead-carbon HUC are described along with its resistance, leakage current, self-discharge and cycle-life characteristics.

Coconut kernel-derived activated carbon as electrode material for electrical double-layer capacitors

Carbonization of milk-free coconut kernel pulp is carried out at low temperatures. The carbon samples are activated using KOH, and electrical double-layer capacitor (EDLC) properties are studied. Among the several samples prepared, activated carbon prepared at 600 A degrees C has a large surface area (1,200 m(2) g(-1)). There is a decrease in surface area with increasing temperature of preparation. Cyclic voltammetry and galvanostatic charge-discharge studies suggest that activated carbons derived from coconut kernel pulp are appropriate materials for EDLC studies in acidic, alkaline, and non-aqueous electrolytes. Specific capacitance of 173 F g(-1) is obtained in 1 M H2SO4 electrolyte for the activated carbon prepared at 600 A degrees C. The supercapacitor properties of activated carbon sample prepared at 600 A degrees C are superior to the samples prepared at higher temperatures.

A 3.8-V earth-abundant sodium battery electrode

Rechargeable lithium batteries have ushered the wireless revolution over last two decades and are now matured to enable green automobiles. However, the growing concern on scarcity and large-scale applications of lithium resources have steered effort to realize sustainable sodium-ion batteries, Na and Fe being abundant and low-cost charge carrier and redox centre, respectively. However, their performance is limited owing to low operating voltage and sluggish kinetics. Here we report a hitherto-unknown material with entirely new composition and structure with the first alluaudite-type sulphate framework, Na2Fe2(SO4)(3), registering the highest-ever Fe3+/ Fe2+ redox potential at 3.8V (versus Na, and hence 4.1V versus Li) along with fast rate kinetics. Rare-metal-free Na-ion rechargeable battery system compatible with the present Li-ion battery is now in realistic scope without sacrificing high energy density and high power, and paves way for discovery of new earth-abundant sustainable cathodes for large-scale batteries.

Co-liposomes comprising a lipidated multivalent RGD-peptide and a cationic gemini cholesterol induce selective gene transfection in alpha v beta 3 and alpha v beta 5 integrin receptor-rich cancer cells

The alpha v beta 3 and alpha v beta 5 integrins, transmembrane glycoprotein receptors, are over-expressed in numerous tumors and in endothelial cells that constitute tumor blood vessels. As this protein selectively binds to the Arg-Gly-Asp (RGD) sequence containing peptides, it is an attractive way to target tumors. Herein we have developed novel formulations for integrin mediated selective gene delivery. These formulations are composed of a novel palmitoylated tetrameric RGD containing scaffold (named RAFT-RGD), cationic gemini cholesterol (GL5) and a natural helper lipid 1,2-dioleoyl-L-alpha-glycero-3-phosphatidylethanolamine (DOPE). We have optimized a co-liposomal formulation to introduce the multivalent RGD-containing macromolecule in GL5: DOPE (GL5D) mixture to produce GL5D-RGD. We have unambiguously shown the selectivity of these formulations towards cancer cells that over express alpha v beta 3 and alpha v beta 5 integrins. Two reporter plasmids, pEGFP-C3 and PGL-3, were employed for the transfection experiments and it was shown that GL5D-RGD Liposomes increased exclusively the transfection in alpha v beta 3 and alpha v beta 5 overexpressing HeLa cells.

Optical properties of an inhomogeneously broadened Lambda V-system with multiple excited states

We present a theoretical model using a density matrix approach to show the influence of multiple excited states on the optical properties of an inhomogeneously broadened Lambda V-system of the Rb-87 D2 line. These closely spaced multiple excited states cause asymmetry in absorption and dispersion profiles. We observe the reduced absorption profiles, due to dressed state interactions of the applied electromagnetic fields, which results the Mollow sideband-like transparency windows. In a room temperature vapor, we obtain a narrow enhanced absorption and steep positive dispersion at the line center when the strengths of control and pump fields are equal. Here, we show how the probe transmittance varies when it passes through the atomic medium. We also discuss the transient behavior of our system which agrees well with the corresponding absorption and dispersion profiles. This study has potential applications in controllability of group velocity, and for optical and quantum information processing.

Diffusion of components via different modes during growth of the A15-V(3)Gaphase

Based on an interdiffusion study using an incremental diffusion couple in the V-Ga binary system, we have shown that V diffuses via the lattice, whereas Ga does so via grain boundaries, for the growth of the V3Ga phase. We estimate the contributions from the two different mechanisms, which are usually difficult to delineate in an interdiffusion study. Available tracer diffusion studies and the atomic arrangement in the crystal structure have been considered for a discussion on the diffusion mechanisms.

t-Na-2(VO)P2O7: A 3.8 V Pyrophosphate Insertion Material for Sodium-Ion Batteries

Pyrophosphate oxyanionic framework compounds offer a great platform to investigate new battery materials. In our continuing effort to explore pyrophosphate cathodes for sodium-ion batteries, we report, for the first time, the synthesis and use of tetragonal Na-2(VO)P2O7 as a potential sodium-ion insertion material. This material can be easily prepared by using a conventional solid-state route at a relatively low temperature of 400 degrees C. Stabilizing as a tetragonal structure with an open framework, the material offers pathways for Na+ diffusion. The as-synthesized material, with no further cathode optimization, yields a reversible capacity (Q) approaching 80 mAh g(-1) (Q(Theoretical) = 93.4 mAh g(-1)) involving a one electron V5+/V4+ redox potential located at 3.8 V (vs. Na/Na+). Furthermore, the material exhibits decent rate kinetics and reversibility. Combining green synthesis and moderate electrochemical properties, t-Na-2(VO)P2O7 is reported as a new addition to the growing family of pyrophosphate cathodes for sodium-ion batteries.

A meshless adaptive multiscale method for fracture

The paper presents a multiscale method for crack propagation. The coarse region is modelled by the differential reproducing kernel particle method. Fracture in the coarse scale region is modelled with the Phantom node method. A molecular statics approach is employed in the fine scale where crack propagation is modelled naturally by breaking of bonds. The triangular lattice corresponds to the lattice structure of the (111) plane of an FCC crystal in the fine scale region. The Lennard-Jones potential is used to model the atom-atom interactions. The coupling between the coarse scale and fine scale is realized through ghost atoms. The ghost atom positions are interpolated from the coarse scale solution and enforced as boundary conditions on the fine scale. The fine scale region is adaptively refined and coarsened as the crack propagates. The centro symmetry parameter is used to detect the crack tip location. The method is implemented in two dimensions. The results are compared to pure atomistic simulations and show excellent agreement. (C) 2014 Elsevier B. V. All rights reserved.

Performance comparison for 12 V lead-carbon hybrid ultracapacitors with substrate-integrated and conventional pasted positive plates

Lead-carbon hybrid ultracapacitors comprise positive lead dioxide plates of the lead-acid battery and negative plates of carbon-based electrical double-layer capacitors (EDLCs). Accordingly, a lead-carbon hybrid ultracapacitor has the features of both the battery and that of an EDLC. In this study, the development and performance comparison between the two types of lead-carbon hybrid ultracapacitors, namely those with substrate-integrated and conventional pasted positive plates, is presented as such a study is lacking in the literature. The study suggests that the faradaic efficiencies for both types of lead-carbon hybrid ultracapacitors are comparable. However, their capacitance values as well as energy and power densities differ significantly. For substrate-integrated positive plate hybrid ultracapacitor, capacitance and energy density values are lower, but power density values are higher than pasted positive plate lead-carbon hybrid ultracapacitors due to their shorter response time. Accordingly, internal resistance values are also lower for substrate-integrated lead-carbon hybrid ultracapacitors. Both types of lead-carbon hybrid ultracapacitors exhibit good cycle life of 100,000 pulse charge-discharge cycles with only a nominal loss in their capacitance values.

Faster computation of the Karhunen-Loeve expansion using its domain independence property

The goal of this work is to reduce the cost of computing the coefficients in the Karhunen-Loeve (KL) expansion. The KL expansion serves as a useful and efficient tool for discretizing second-order stochastic processes with known covariance function. Its applications in engineering mechanics include discretizing random field models for elastic moduli, fluid properties, and structural response. The main computational cost of finding the coefficients of this expansion arises from numerically solving an integral eigenvalue problem with the covariance function as the integration kernel. Mathematically this is a homogeneous Fredholm equation of second type. One widely used method for solving this integral eigenvalue problem is to use finite element (FE) bases for discretizing the eigenfunctions, followed by a Galerkin projection. This method is computationally expensive. In the current work it is first shown that the shape of the physical domain in a random field does not affect the realizations of the field estimated using KL expansion, although the individual KL terms are affected. Based on this domain independence property, a numerical integration based scheme accompanied by a modification of the domain, is proposed. In addition to presenting mathematical arguments to establish the domain independence, numerical studies are also conducted to demonstrate and test the proposed method. Numerically it is demonstrated that compared to the Galerkin method the computational speed gain in the proposed method is of three to four orders of magnitude for a two dimensional example, and of one to two orders of magnitude for a three dimensional example, while retaining the same level of accuracy. It is also shown that for separable covariance kernels a further cost reduction of three to four orders of magnitude can be achieved. Both normal and lognormal fields are considered in the numerical studies. (c) 2014 Elsevier B.V. All rights reserved.

On the Origin of Steep I-V Nonlinearity in Mixed-Ionic-Electronic-Conduction-Based Access Devices

Numerical modeling is used to explain the origin of the large ON/OFF ratios, ultralow leakage, and high ON-current densities exhibited by back-end-of-the-line-friendly access devices based on copper-containing mixed-ionic-electronic-conduction (MIEC) materials. Hall effect measurements confirm that the electronic current is hole dominated; a commercial semiconductor modeling tool is adapted to model MIEC. Motion of large populations of copper ions and vacancies leads to exponential increases in hole current, with a turn-ON voltage that depends on material bandgap. Device simulations match experimental observations as a function of temperature, electrode aspect ratio, thickness, and device diameter.

On linear series and a conjecture of D. C. Butler

Let C be a smooth irreducible projective curve of genus g and L a line bundle of degree d generated by a linear subspace V of H-0 (L) of dimension n+1. We prove a conjecture of D. C. Butler on the semistability of the kernel of the evaluation map V circle times O-C -> L and obtain new results on the stability of this kernel. The natural context for this problem is the theory of coherent systems on curves and our techniques involve wall crossing formulae in this theory.

Observation of coherent population trapping in a V-type two-electron system

We observe coherent population trapping (CPT) in a two-electron atom-Yb-174-using the S-1(0), F= 0 -> P-3(1), F `= 1 transition. CPT is not possible for such a transition according to one-electron theory because the magnetic sublevels form a V-type system, but in a two-electron atom like Yb, the interaction of the electrons transforms the level structure into a V-type system, which allows the formation of a dark state and hence the observation of CPT. Since the two levels involved are degenerate, we use a magnetic field to lift the degeneracy. The single fluorescence dip then splits into five dips-the central unshifted one corresponds to coherent population oscillation, while the outer four are due to CPT. The linewidth of the CPT resonance is about 300 kHz and is limited by the natural linewidth of the excited state, which is to be expected because the excited state is involved in the formation of the dark state.

Use of Data Driven Techniques for Short Lead Time Streamflow Forecasting in Mahanadi basin

Streamflow forecasts at daily time scale are necessary for effective management of water resources systems. Typical applications include flood control, water quality management, water supply to multiple stakeholders, hydropower and irrigation systems. Conventionally physically based conceptual models and data-driven models are used for forecasting streamflows. Conceptual models require detailed understanding of physical processes governing the system being modeled. Major constraints in developing effective conceptual models are sparse hydrometric gauge network and short historical records that limit our understanding of physical processes. On the other hand, data-driven models rely solely on previous hydrological and meteorological data without directly taking into account the underlying physical processes. Among various data driven models Auto Regressive Integrated Moving Average (ARIMA), Artificial Neural Networks (ANNs) are most widely used techniques. The present study assesses performance of ARIMA and ANNs methods in arriving at one-to seven-day ahead forecast of daily streamflows at Basantpur streamgauge site that is situated at upstream of Hirakud Dam in Mahanadi river basin, India. The ANNs considered include Feed-Forward back propagation Neural Network (FFNN) and Radial Basis Neural Network (RBNN). Daily streamflow forecasts at Basantpur site find use in management of water from Hirakud reservoir. (C) 2015 The Authors. Published by Elsevier B.V.