The prop-2-ynyloxy carbonyl function (POC): A new amino-protecting group removable from sulfur-containing peptides by ultrasonic irradiation with tetrathiomolybdate under mild and neutral conditions

The prop-2-ynyloxy carbonyl function (POC) which can be cleaved under mild and neutral conditions in the presence of benzyltriethylammonium tetrathiomolybdate has been developed as a new protecting group for amines. (C) 1999 Elsevier Science Ltd. All rights reserved.

Microbially induced flotation of alumina, silica/calcite from haematite

Selective separation of haematite from alumina and silica/calcite was achieved through microbiologically induced flotation and flocculation in presence of Bacillus subtilis. Bacterial metabolites containing extracellular proteins were characterized from mineral-grown bacterial cell free extract. Bacteria can adhere to mineral surfaces and influence subsequent flotation of the minerals. Cells and metabolic products of bacteria were used in flotation, flocculation and adsorption studies on oxide minerals. Bacteria functions as a stronger depressant for haematite. Selective affinity of the bacterial cells towards the mineral surface was observed through adsorption studies. Bacterial byproduct like extracellular protein (EP) was isolated from bacteria. The protein profile of the EP of bacterial cells grown in presence and absence of minerals (haematite, corundum, quartz and calcite) was also studied. The role of such proteins in selective mineral separation was demonstrated through microbially induced selective flotation. This study has demonstrated the utility and amenability of microbially induced mineral beneficiation through the use of bacterially generated metabolic products and mineral-grown bacterial cells. (C) 2011 Elsevier B.V. All rights reserved.

Insulator-metal transition and magnetoresistance of La0.5Ca0.5MnOy induced by tuning the oxygen content

The oxygen content of La0.5Ca0.5MnOy was tuned by annealing the samples at high temperatures in flowing nitrogen with graphite powder nearby. The reduction of oxygen content has dramatic effect on the electrical transport and magnetic properties. The samples with y=2.983, 2.83, and 2.803 show an insulator-metal transition, and an unusual temperature and magnetic-field dependence of the magnetoresistance. The paramagnetic-ferromagnetic transition also shifts to lower temperatures and the antiferromagnetic transition at lower temperature is suppressed. The results are discussed in terms of the effect of oxygen vacancies on the various properties of La0.5Ca0.5MnOy. (C) 2002 American Institute of Physics.

Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites: Role of cation-guest binding

Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenyleylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20% ee and 55% de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum similar to10% ee).

Pressure-induced phase transitions in alpha-ZrMo2O8

We report high-pressure Raman, infrared (IR), and optical-absorption spectra of alpha-ZrMo2O8 (trigonal) up to 38 GPa at room temperature. The spectroscopic studies are consistent with diffraction results that show that alpha-ZrMo2O8 transforms into delta-ZrMo2O8 (monoclinic) at about 1 GPa and the delta phase converts to the epsilon phase (trielinic) at about 2.0 GPa. Optical-absorption measurements give an estimate of the band gap of about 0.6 eV at the lowest pressure. Band-gap changes with pressure are confirmed with visual observations. ZrMo2O8 changes from transparent at 5 GPa to yellow at 10 GPa, red at 18 GPa, and at about 30 GPa it becomes opaque.

Synthesis and metallic probe induced conductance of Au tipped ultranarrow PbS rods

Au tipped ultranarrow PbS nanorods are synthesized. DFT electronic structure calculations and transport studies show that Au probes modify the nature and energies of PbS nanorod orbitals creating efficient electron conduction channels for enhanced conductance even at low applied bias.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti(62.5)Si(37.5) thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe(+) ion beam to an ion fluence of about 10(16) ions-cm(-2). Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti(5)Si(3) intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

Stress induced phase transition in a monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Biaxial strain induced electrical inhomogenities and phase separation in the ferromagnetic metallic phase in thin films of La0.7Ca0.3MnO3: A scanning tunneling potentiometry/spectroscopy study

We have investigated the effect of biaxial strain on local electrical/electronic properties in thin films of La0.7Ca0.3MnO3 with varying degrees of biaxial strain in them. The local electrical properties were investigated as a function of temperature by scanning tunneling spectroscopy (STS) and scanning tunneling potentiometry (STP), along with the bulk probe like conductance fluctuations.The results indicate a positive correlation between the lattice mismatch biaxial strain and the local electrical/electronic inhomogenities observed in the strained sample. This is plausible since the crystal structure of the manganites interfere rather strongly with the magnetic/electronic degrees of freedom. Thus even a small imbalance (biaxial strain) can induce significant changes in the electrical properties of the system.

Field Induced Dielectric Properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 Thin Films

DC electric field induced dielectric properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) thin films were studied as a function of frequency at different temperatures. It was observed that the dielectric constant (ε) and dissipation factor (tanδ) were decreased in presence of bias field. The temperature of dielectric maxima was found to increase with increasing bias level. The low temperature (

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

BCS-BEC crossover induced by a synthetic non-Abelian gauge field

We investigate the ground state of interacting spin-1/2 fermions in three dimensions at a finite density (rho similar to k(F)(3)) in the presence of a uniform non-Abelian gauge field. The gauge-field configuration (GFC) described by a vector lambda equivalent to (lambda(x),lambda(y),lambda(z)), whose magnitude lambda determines the gauge coupling strength, generates a generalized Rashba spin-orbit interaction. For a weak attractive interaction in the singlet channel described by a small negative scattering length (k(F)vertical bar a(s)vertical bar less than or similar to 1), the ground state in the absence of the gauge field (lambda = 0) is a BCS (Bardeen-Cooper-Schrieffer) superfluid with large overlapping pairs. With increasing gauge-coupling strength, a non-Abelian gauge field engenders a crossover of this BCS ground state to a BEC (Bose-Einstein condensate) of bosons even with a weak attractive interaction that fails to produce a two-body bound state in free vacuum (lambda = 0). For large gauge couplings (lambda/k(F) >> 1), the BEC attained is a condensate of bosons whose properties are solely determined by the Rashba gauge field (and not by the scattering length so long as it is nonzero)-we call these bosons ``rashbons.'' In the absence of interactions (a(s) = 0(-)), the shape of the Fermi surface of the system undergoes a topological transition at a critical gauge coupling lambda(T). For high-symmetry GFCs we show that the crossover from the BCS superfluid to the rashbon BEC occurs in the regime of lambda near lambda(T). In the context of cold atomic systems, these results make an interesting suggestion of obtaining BCS-BEC crossover through a route other than tuning the interaction between the fermions.

Defining the ‘modified Griffin plot’ in vortex-induced vibration: revealing the effect of Reynolds number using controlled damping

In the present work, we study the transverse vortex-induced vibrations of an elastically mounted rigid cylinder in a fluid flow. We employ a technique to accurately control the structural damping, enabling the system to take on both negative and positive damping. This permits a systematic study of the effects of system mass and damping on the peak vibration response. Previous experiments over the last 30 years indicate a large scatter in peak-amplitude data ($A^*$) versus the product of mass–damping ($\alpha$), in the so-called ‘Griffin plot’. A principal result in the present work is the discovery that the data collapse very well if one takes into account the effect of Reynolds number ($\mbox{\textit{Re}}$), as an extra parameter in a modified Griffin plot. Peak amplitudes corresponding to zero damping ($A^*_{{\alpha}{=}0}$), for a compilation of experiments over a wide range of $\mbox{\textit{Re}}\,{=}\,500-33000$, are very well represented by the functional form $A^*_{\alpha{=}0} \,{=}\, f(\mbox{\textit{Re}}) \,{=}\, \log(0.41\,\mbox{\textit{Re}}^{0.36}$). For a given $\mbox{\textit{Re}}$, the amplitude $A^*$ appears to be proportional to a function of mass–damping, $A^*\propto g(\alpha)$, which is a similar function over all $\mbox{\textit{Re}}$. A good best-fit for a wide range of mass–damping and Reynolds number is thus given by the following simple expression, where $A^*\,{=}\, g(\alpha)\,f(\mbox{\textit{Re}})$: \[ A^* \,{=}\,(1 - 1.12\,\alpha + 0.30\,\alpha^2)\,\log (0.41\,\mbox{\textit{Re}}^{0.36}). \] In essence, by using a renormalized parameter, which we define as the ‘modified amplitude’, $A^*_M\,{=}\,A^*/A^*_{\alpha{=}0}$, the previously scattered data collapse very well onto a single curve, $g(\alpha)$, on what we refer to as the ‘modified Griffin plot’. There has also been much debate over the last three decades concerning the validity of using the product of mass and damping (such as $\alpha$) in these problems. Our results indicate that the combined mass–damping parameter ($\alpha$) does indeed collapse peak-amplitude data well, at a given $\mbox{\textit{Re}}$, independent of the precise mass and damping values, for mass ratios down to $m^*\,{=}\,1$.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti62.5Si37.5 thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe+ ion beam to an ion fluence of about 1016 ions-cm−2. Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti5Si3 intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.