A new search for the atomic EDM of 129Xe at FRM-II

Permanent electric dipole moments (EDMs) arise due to the breaking of time-reversal or, equivalently, CP-symmetry. Although EDM searches have so far only set upper limits, which are many orders of magnitude larger than Standard Model (SM) predictions, the motivation for more sensitive searches is stronger than ever. A new effort at FRM-II incorporating ¹²⁹Xe and ³He as a co-magnetometer can potentially improve the current limit. The noble gas mixture of ¹²⁹Xe and ³He is simultanously polarized by spin-exchange optical pumping and then transferred into a high-performance magnetically shielded room. Inside, both species can freely precess in the presence of applied magnetic and electric fields. The precession signals are detected by LTc SQUID sensors. In EDM cells with silicon electrodes we observed spin lifetimes in excess of 2500 s without and with high-voltage applied. This meets one requirement to achieve our goal of improving the EDM limit on ¹²⁹Xe by several orders of magnitude.     

Alkyl-CoA disulfides as inhibitors and mechanistic probes for FabH enzymes

The first step of the reaction catalyzed by the homodimeric FabH from a dissociated fatty acid synthase is acyl transfer from acyl-CoA to an active site cysteine. We report that C1 to C10 alkyl-CoA disulfides irreversibly inhibit Escherichia coli FabH (ecFabH) and Mycobacterium tuberculosis FabH with relative efficiencies that reflect these enzymes' differential acyl-group specificity. Crystallographic and kinetic studies with MeSSCoA show rapid inhibition of one monomer of ecFabH through formation of a methyl disulfide conjugate with this cysteine. Reaction of the second subunit with either MeSSCoA or acetyl-CoA is much slower. In the presence of malonyl-ACP, the acylation rate of the second subunit is restored to that of the native ecFabH. These observations suggest a catalytic model in which a structurally disordered apo-ecFabH dimer orders on binding either the first substrate, acetyl-CoA, or the inhibitor MeSSCoA, and is restored to a disordered state on binding of malonyl-ACP.     

Control of electron transport using redox‐active core dendrimers

We are constructing a model system to elucidate the molecular structure‐property relationships for attenuation of electron transfer (e.g. electron encapsulation). This information is relevant in bio‐electron transfer schemes and in emerging molecular electronics schemes such as storage of information using individual molecules. Our system consists of an inorganic cluster surrounded by dendritic ligands which act as an organic coating. Although the electrochemical and photophysical properties of a variety of metal clusters have been established, very little has been described on the chemistry on metal clusters.     

Electrical and structural properties enhancement in plasticized high Tg polymers using metal salts

Plasticized polymer electrolyte composite has been prepared in the form of a film by solution casting method. Poly (ethyl methacrylate) (PEMA) acts as a host polymer and is doped with Sodium Iodide (NaI). Ethylene carbonate (EC) added as a plasticizer and also enhances amorphicity of the polymer electrolyte. The electrical conductivity of the PEMA+NaI was evaluated using complex impedance spectroscopy. Maximum ionic conductivity obtained at room temperature was 8.75 × 10^?6 S/cm with the composition of PEMA: NaI (30%) + 60% EC. The conductivity further increased with increase in temperature and moved up to 5.8 × 10^?5 S/cm. Scanning electron microscopy was used to study the surface morphology of the composite film. Fourier transform infrared ray and X-ray diffraction data confirmed the complexation of material.     

FTIR microscopy of biological cells and tissue: data analysis using resonant Mie scattering (RMieS) EMSC algorithm

Transmission and transflection infrared microscopy of biological cells and tissue suffer from significant baseline distortions due to scattering effects, predominantly resonant Mie scattering (RMieS). This scattering can also distort peak shapes and apparent peak positions making interpretation difficult and often unreliable. A correction algorithm, the resonant Mie scattering extended multiplicative signal correction (RMieS-EMSC), has been developed that can be used to remove these distortions. The correction algorithm has two key user defined parameters that influence the accuracy of the correction. The first is the number of iterations used to obtain the best outcome. The second is the choice of the initial reference spectrum required for the fitting procedure. The choice of these parameters influences computational time. This is not a major concern when correcting individual spectra or small data sets of a few hundred spectra but becomes much more significant when correcting spectra from infrared images obtained using large focal plane array detectors which may contain tens of thousands of spectra. In this paper we show that, classification of images from tissue can be achieved easily with a few (<10) iterations but a reliable interpretation of the biochemical differences between classes could require more iterations. Regarding the choice of reference spectrum, it is apparent that the more similar it is to the pure absorption spectrum of the sample, the fewer iterations required to obtain an accurate corrected spectrum. Importantly however, we show that using three different non-ideal reference spectra, the same unique correction solution can be obtained.     

Fabrication of surfactant-free quercetin-loaded PLGA nanoparticles: evaluation of hepatoprotective efficacy by nuclear scintigraphy

Journal of Nanoparticle Research - This paper investigates the global nanotechnology and nanoscience (NN) indicators in a developmental context, during three 5-year periods from 2000 to 2014....     

A new synthesis of aryl hetaryl ketones via SRN1 reactions of halogenated heterocycles with potassiophenylacetonitrile followed by phase-transfer catalyzed decyanation

Reaction of halogenated pyridines, quinolines, pyrimidines, and pyrazines with potassiophenylacetonitrile ( 5 ) in liquid ammonia under near-uv irradiation affords secondary nitriles, which then undergo oxidative decyanation under phase-transfer catalytic conditions to afford aryl hetaryl ketones in excellent yields.     

Electrolysis of sodium chloride using composite poly(styrene-co-divinylbenzene) cation exchange membranes

Composite cation exchange membranes are prepared from cross-linked styrene-divinylbenzene copolymers for the electrolysis of sodium chloride to produce sodium hydroxide and chlorine by selective removal of sodium ions. It is prepared from a syrup of the polymer using dual initiating system and is modified with chloroacetic acid to introduce acid functional groups (COO⁻) on its surface. The effect of the modification is confirmed by FTIR, SEM, contact angle, water content, and ion exchange capacity measurements. The performance of the membrane has been evaluated in terms of current efficiency and power consumption and the effect of current density, salt concentration and flow rate on efficiency has been studied. Our membrane has an ion exchange capacity of 0.833 meq./g which is close to that of the commercially available Nafion-117 membrane having an ion exchange capacity 0.9 meq./g. The Nafion-117 used for electrodialysis of sodium sulfate has a current efficiency of around 90% and specific energy consumption of 0.1 kW/mol at 2N concentration of the salt at 1000 A/m². Our membrane used for electrodialysis of sodium chloride has a current efficiency of 93% and a power consumption of around 0.3122 kW/mol at the same concentration of salt and at a current density of 254 A/m². The two-dimensional space-charge model in cylindrical coordinates has been solved semi-analytically to obtain the effective wall potential and pore size of the membrane which are difficult to measure directly. The experimentally obtained solute flux and current density have been fitted to the model and optimum values of effective wall potential and pore diameter have been determined to be 98.5 mV and 0.8 nm, respectively.     

Separate entrance and exit portals for ligand traffic in Mycobacterium tuberculosis FabH

Mycobacterium tuberculosis FabH initiates type II fatty acid synthase-catalyzed formation of the long chain (C(16)-C(22)) acyl-coenzyme A (CoA) precursors of mycolic acids, which are major constituents of the bacterial cell envelope. Crystal structures of M. tuberculosis FabH (mtFabH) show the substrate binding site to be a buried, extended L-shaped channel with only a single solvent access portal. Entrance of an acyl-CoA substrate through the solvent portal would require energetically unfavorable reptational threading of the substrate to its reactive position. Using a class of FabH inhibitors, we have tested an alternative hypothesis that FabH exists in an "open" form during substrate binding and product release, and a "closed" form in which catalysis and intermediate steps occur. This hypothesis is supported by mass spectrometric analysis of the product profile and crystal structures of complexes of mtFabH with these inhibitors.     

Phase evolution studies of sol�Cgel derived lead zirconate titanate (PZT) nanopowder using X-ray diffraction and X-ray photoelectron spectroscopy

We report here the formation of single phase lead zirconate titanate (PZT) nanopowder with composition Pb(Zr_0.52Ti_0.48)O₃ and average crystallite size 12?C20?nm, synthesized by sol?Cgel process. The phase evolution of PZT gel powder, heat treated at temperatures 550, 650 and 800°C was monitored by X-ray diffraction (XRD) and X-ray photo-electron spectroscopy (XPS). The high resolution XPS spectra of Pb4f, Zr3d, Ti2p and O1s show that PZT with pure perovskite structure is obtained at 800°C while at lower temperatures pyrochlore phase co-exists with perovskite phase. The XRD results also support this analysis. We have also identified the pyrochlore phase using XPS by analyzing the corresponding variations in the FWHM values, peak positions and the separation between the spin doublets of Pb, Zr and Ti associated with it. The composition of the final powder obtained with pure perovskite structure is calculated and is close to the designed value.