13C-1H HSQC Experiment of Probe Molecules Aligned in Thermotropic Liquid Crystals: Sensitivity and Resolution Enhancement in the Indirect Dimension

The spectra of molecules oriented in liquid crystalline media are dominated by partially averaged dipolar couplings. In the 13C–1H HSQC, due to the inefficient hetero-nuclear dipolar decoupling in the indirect dimension, normally carried out by using a π pulse, there is a considerable loss of resolution. Furthermore, in such strongly orienting media the 1H–1H and 13C–1H dipolar couplings leads to fast dephasing of transverse magnetization causing inefficient polarization transfer and hence the loss of sensitivity in the indirect dimension. In this study we have carried out 13C–1H HSQC experiment with efficient polarization transfer from 1H to 13C for molecules aligned in liquid crystalline media. The homonuclear dipolar decoupling using FFLG during the INEPT transfer delays and also during evolution period combined with the π pulse heteronuclear decoupling in the t1 period has been applied. The studies showed a significant reduction in partially averaged dipolar couplings and thereby enhancement in the resolution and sensitivity in the indirect dimension. This has been demonstrated on pyridazine and pyrimidine oriented in the liquid crystal. The two closely resonating carbons in pyrimidine are better resolved in the present study compared to the earlier work [H.S. Vinay Deepak, Anu Joy, N. Suryaprakash, Determination of natural abundance 15N–1H and 13C–1H dipolar couplings of molecules in a strongly orienting media using two-dimensional inverse experiments, Magn. Reson. Chem. 44 (2006) 553–565].

Giant photoinduced optical bleaching at room and liquid helium temperatures in Sb/As(2)S(3) multilayered films

We report the observation of giant photo induced optical bleaching in Sb/As(2)S(3) multilayered film at room and liquid He temperatures, when irradiated with 532 nm laser at moderate intensities. The experimental results show a dramatic increase in transmittance near the band gap regime at both the temperatures; however the rates at which transmission change occurs are rather slow at low temperature. The huge change in transmission is due to the photo induced intermixing of As(2)S(3) layer with Sb. Our XPS measurements show that photo induced intermixing occurs through the wrong homopolar bonds, which under actinic light illumination are converted into energetically favored hetropolar bonds. (C) 2011 Elsevier B.V. All rights reserved.

Insulating State and Breakdown of Fermi Liquid Description in Molecular-Scale Single-Crystalline Wires of Gold

Electrical transport measurements on ultrathin single-crystalline Au nanowires, synthesized via a wet chemical route, show an unexpected insulating behavior. The linear response electrical resistance exhibits a power-law dependence on temperature. In addition, the variation of current over a wide range of temperature and voltage obeys a universal scaling relation that provides compelling evidence for a non-Fermi liquid behavior. Our results demonstrate that the quantum ground state In ultrathin nanowires of simple metallic systems can be radically different from their bulk counterparts and can be described In terms of a Tomonaga-Luttinger liquid (TLL), in the presence of remarkably strong electron-electron interactions.

Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

Cold model study of local liquid holdup in the dropping zone using x-ray

It is important to know and to quantify the liquid holdups both dynamic and static at local levels as it will lead to understand various blast furnace phenomena properly such as slag/metal.gas.solid reactions, gas flow behaviour and interfacial area between the gas/solid/liquid. In the present study, considering the importance of local liquid holdup and non-availability of holdup data in these systems, an attempt has been made to quantify the local holdups in the dropping and around raceway zones in a cold model study using a non-wetting packing for liquid. In order to quantify the liquid holdups at microscopic level, a previously developed technique, X-ray radiography, has been used. It is observed that the liquid flows in preferred paths or channels which carry droplets/rivulets. It has been found that local holdup in some regions of the packed bed is much higher than average at a particular flow rate and this can have important consequences for the correct modelling of such systems.

Thermodynamics of oxygen in liquid copper-tin alloys

The activity coefficients of oxygen in copper-tin alloys at 1 1 00°C have been measured by two different equilibrium methodsthe cell Pt, Ni + NiO I ZrOz solid electrolyte I O[Cu + Sn], cermet. Pt and the equilibrium between Cu + Sn alloys and SnO + SiO, slags established via SnO vapour. The results from both types of measurement confirm the work of Block and co-workers and show that other data are in error. The deoxidation equilibria for Sn in liquid copper, with solid SnO, as deoxidation product, have been evaluated at temperatures of interest in copper smelting.

Thermodynamics of oxygen in liquid copper, lead and copper lead alloys

Solid oxide galvanic cells of the type Pt, Ni-NiO I Solid electrolyte ( Ometa,, Cermet. Pt were used to measure the activity coefficient of oxygen in liquid copper at 11 00 and 1 300eC, and in lead at 11 00'C. Similar cells were used to study the activity coefficient of oxygen in the whole range of Cu + Pb alloys at 1100'C and in lead-rich alloys at 900 and 750'C.The results obtained are discussed in terms of proposed solution models. An equation based on the formation of 'species' of the form M,O in solutions of oxygen in binary alloys is shown to fit the experimental data.

Thermodynamic study of oxygen in liquid lead tin alloys

The activity coefficients of oxygen in liquid lead-tin alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells Pt, Ni-NiO I Zr02 Solid electrolyte I 0 (Pb + Sn), Cermet, Pt Pt, Fe-FeO I Zr02 Solid electrolyte I O(Pb + Sn), Cermet, Pt Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys.The relative partial molar enthalpy and entropy of oxygen ?t 1 atom per cent in the alloys have been calculated from ttva variation of the activity coefficient with temperature. The addition of tin to an unsaturated solution of oxygen in lead is shown to decrease significantly both the partial molar enthalpy and entropy of oxygen. As the measurements were restricted to a narrow range between 750-1100'C in lead-rich alloys, however, the pronounced variation of the partial molar enthalpy of oxygen with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Deoxidation of liquid copper: effect of phosphorus on oxygen activity

An analysis of the deoxidation of liquid copper is made by use of an Ellingham-type diagram, which incorporates data now available on interactions between copper and the deoxidant in solution. To make the diagram more quantitative information is required on interactions between oxygen and the deoxidants and the activities of component oxides in slags of interest in copper smelting.