Specroelectrochemical, Switching Kinetics, and Chronoamperometric Studies of Dibenzyl Derivative of Poly(3,4-propylenedioxythiophene) Thin-Film-Based Electrochromic Device

The dibenzyl derivative of poly(3,4-propylenedioxythiophene) (PProDOT-Bz(2)) thin film is deposited onto ITO-coated glass substrate by electropolymerization technique. The electropolymerization of ProDOT-Bz(2) is carried out by a three-electrode electrochemical cell. The cyclic voltammogram shows the redox properties of electrochemically prepared films deposited at different scan rates. The thin films prepared were characterized for its morphological properties to study the homogeniety. Classic six-layer structure of PProDOT-Bz(2) electrochromic device using this material was fabricated and reported for the first and its characterizations such as spectroelectrochemical, switching kinetics, and chronoamperometric studies are performed. The color contrast of the thin film and the device achieved are 64 and 40%, respectively, at lambda(max) (628 nm). The switching time is recorded and the observed values are 5 s from the coloring state to the bleaching state and vice versa. The chronoamperometry shows that the device performed up to 400 cycles, and it is capable of working up to 35 cycles without any degradation. (C) 2014 Wiley Periodicals, Inc.

Rapid, microwave-assisted synthesis of Gd2O3 and Eu:Gd2O3 nanocrystals: characterization, magnetic, optical and biological studies

Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.

Azide and Alkyne Terminated Polybutadiene Binders: Synthesis, Cross-linking, and Propellant Studies

In composite solid propellants, the fuel and oxidizer are held together by a polymer binder. Among the different types of polymeric binders used in solid propellants, hydroxyl terminated polybutadiene (HTPB) is considered as the most versatile. HTPB is conventionally cured using isocyanates to form polyurethanes. However, the incompatibility of isocyanates with energetic oxidizers such as ammonium dinitramide and hydrazinium nitroformate, the short pot life of the propellant slurry, and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of HTPB based propellant. With an aim of resolving these problems, HTPB was chemically transformed to azidoethoxy carbonyl amine terminated polybutadiene and propargyloxy carbonyl amine terminated polybutadiene by adopting appropriate synthesis strategies and characterizing them by spectroscopic and chromatographic techniques. This is the first report on 1,3-dipolar addition reaction involving azide and alkyne end groups for cross-linking HTPB. The blend of these two polymers underwent curing under mild temperature (60 degrees C) conditions through 1,3-dipolar cycloaddition reaction resulting in triazoletriazoline networks. The curing parameters were studied using differential scanning calorimetry. The kinetic parameter, viz., activation energy, was computed to be 107.6 kJ/mol, the preexponential factor was 2.79 x 10(12) s-(1), and the rate constant at 60 degrees C was computed to be 3.64 x 10-(5) s-(1). The cure profile at a given temperature was predicted using the kinetic parameters. Rheological studies revealed that the gel time for curing through the 1,3-dipolar addition is 280 min compared to 120 min for curing through the urethane route. The mechanical properties of the resultant cured polybutadiene network were superior to those of polyurethanes. The cured triazolinetriazole polymer network exhibited biphasic morphology with two glass transitions (T-g) at -56 and 42 degrees C in contrast to the polyurethane which exhibited a single transition at -60 degrees C. This was corroborated by associated morphological changes observed by scanning probe microscopy. The propellant processed using this binder has the advantages of improved pot life as indicated by the end of the mix viscosity which is 165 Pas as compared with 352 Pas for the polyurethane system along with a slow build- up rate. The mechanical properties of the propellant are superior to polyurethane with an improvement of 14% in tensile strength, 22% enhancement in elongation at break, and 12% in modulus.

Dynamics of ribonuclease A and ribonuclease S: Computational and experimental studies

RNase S is a complex consisting of two proteolytic fragments of RNase A: the S peptide (residues 1-20) and S protein (residues 21-124). RNase S and RNase A have very similar X-ray structures and enzymatic activities. previous experiments have shown increased rates of hydrogen exchange and greater sensitivity to tryptic cleavage for RNase S relative to RNase A. It has therefore been asserted that the RNase S complex is considerably more dynamically flexible than RNase A. In the present study we examine the differences in the dynamics of RNaseS and RNase A computationally, by MD simulations, and experimentally, using trypsin cleavage as a probe of dynamics. The fluctuations around the average solution structure during the simulation were analyzed by measuring the RMS deviation in coordinates. No significant differences between RNase S and RNase A dynamics were observed in the simulations. We were able to account for the apparent discrepancy between simulation and experiment by a simple model, According to this model, the experimentally observed differences in dynamics can be quantitatively explained by the small amounts of free S peptide and S protein that are present in equilibrium with the RNase S complex. Thus, folded RNase A and the RNase S complex have identical dynamic behavior, despite the presence of a break in polypeptide chain between residues 20 and 21 in the latter molecule. This is in contrast to what has been widely believed for over 30 years about this important fragment complementation system.

Regolith mass balance inferred from combined mineralogical, geochemical and geophysical studies: Mule Hole gneissic watershed, South India

The aim of this study is to propose a method to assess the long-term chemical weathering mass balance for a regolith developed on a heterogeneous silicate substratum at the small experimental watershed scale by adopting a combined approach of geophysics, geochemistry and mineralogy. We initiated in 2003 a study of the steep climatic gradient and associated geomorphologic features of the edge of the rifted continental passive margin of the Karnataka Plateau, Peninsular India. In the transition sub-humid zone of this climatic gradient we have studied the pristine forested small watershed of Mule Hole (4.3 km(2)) mainly developed on gneissic substratum. Mineralogical, geochemical and geophysical investigations were carried out (i) in characteristic red soil profiles and (ii) in boreholes up to 60 m deep in order to take into account the effect of the weathering mantle roots. In addition, 12 Electrical Resistivity Tomography profiles (ERT), with an investigation depth of 30 m, were generated at the watershed scale to spatially characterize the information gathered in boreholes and soil profiles. The location of the ERT profiles is based on a previous electromagnetic survey, with an investigation depth of about 6 m. The soil cover thickness was inferred from the electromagnetic survey combined with a geological/pedological survey. Taking into account the parent rock heterogeneity, the degree of weathering of each of the regolith samples has been defined using both the mineralogical composition and the geochemical indices (Loss on Ignition, Weathering Index of Parker, Chemical Index of Alteration). Comparing these indices with electrical resistivity logs, it has been found that a value of 400 Ohm m delineates clearly the parent rocks and the weathered materials, Then the 12 inverted ERT profiles were constrained with this value after verifying the uncertainty due to the inversion procedure. Synthetic models based on the field data were used for this purpose. The estimated average regolith thickness at the watershed scale is 17.2 m, including 15.2 m of saprolite and 2 m of soil cover. Finally, using these estimations of the thicknesses, the long-term mass balance is calculated for the average gneiss-derived saprolite and red soil. In the saprolite, the open-system mass-transport function T indicates that all the major elements except Ca are depleted. The chlorite and biotite crystals, the chief sources for Mg (95%), Fe (84%), Mn (86%) and K (57%, biotite only), are the first to undergo weathering and the oligoclase crystals are relatively intact within the saprolite with a loss of only 18%. The Ca accumulation can be attributed to the precipitation of CaCO3 from the percolating solution due to the current and/or the paleoclimatic conditions. Overall, the most important losses occur for Si, Mg and Na with -286 x 10(6) mol/ha (62% of the total mass loss), -67 x 10(6) mol/ha (15% of the total mass loss) and -39 x 10(6) mol/ha (9% of the total mass loss), respectively. Al, Fe and K account for 7%, 4% and 3% of the total mass loss, respectively. In the red soil profiles, the open-system mass-transport functions point out that all major elements except Mn are depleted. Most of the oligoclase crystals have broken down with a loss of 90%. The most important losses occur for Si, Na and Mg with -55 x 10(6) mol/ha (47% of the total mass loss), -22 x 10(6) mol/ha (19% of the total mass loss) and -16 x 10(6) mol/ha (14% of the total mass loss), respectively. Ca, Al, K and Fe account for 8%, 6%, 4% and 2% of the total mass loss, respectively. Overall these findings confirm the immaturity of the saprolite at the watershed scale. The soil profiles are more evolved than saprolite but still contain primary minerals that can further undergo weathering and hence consume atmospheric CO2.

Variable-Temperature EPR and Transport Studies on Poly(4,4'-methylenedianiline): Evidence for Bipolarons

The correlation between magnetic and transport properties is examined by studying poly(4,4'-methylenedianiline)(PMDA) salts and their bases using EPR and conductivity measurements. Five different PMDA salts (doped polymers)were prepared by chemical polymerization of 4,4'-methylenedianiline using different protonic acids. The PMDA bases were obtained by dedoping the salts using ammonium hydroxide. Ambient temperature electrical conductivity measurements show evidence for the doped PMDA system to be highly disordered. The EPR spectra of the samples were recorded in the range 20-200 "C, and the results were analyzed on the basis of the polaron-bipolaron model, which is typical of nondegenerate systems. Both PMDA salts and their bases consist of self-trapped, highly mobile polarons or radical cations. EPR studies on PMDA salts show evidence for the presence of thermally activated and temperature independent (or Pauli type) paramagnetism while the bases show thermally activated, Pauli and Curie-Weiss types of paramagnetism. The paramagnetism arises due to polarons.It is proposed that charge transport takes place through both polarons and bipolarons.

Structural and functional studies of Bacillus stearothermophilus serine hydroxymethyltransferase: the role of Asn(341), Tyr(60) and Phe(351) in tetrahydrofolate binding

SHMT (serine hydoxymethyltransferase), a type I pyridoxal 5'-phosphate-dependent enzyme, catalyses the conversion of L-serine and THF (tetrahydrofolate) into glycine and 5,10-methylene THE SHMT also catalyses several THF-independent side reactions such as cleavage of P-hydroxy amino acids, trans-amination, racemization and decarboxylation. In the present study, the residues Asn(341), Tyr(60) and Phe(351), which are likely to influence THF binding, were mutated to alanine, alanine and glycine respectively, to elucidate the role of these residues in THF-dependent and -independent reactions catalysed by SHMT. The N341A and Y60A bsSHMT (Bacillus stearothermophilus SHMT) mutants were inactive for the THF-dependent activity, while the mutations had no effect on THF-independent activity. However, mutation of Phe(351) to glycine did not have any effect oil either of the activities. The crystal structures of the glycine binary complexes of the mutants showed that N341A bsSHMT forms an external aldimine as in bsSHMT, whereas Y60A and F351G bsSHMTs exist as a Mixture of internal/external aldimine and gem-diamine forms. Crystal structures of all of the three Mutants obtained in the presence of L-allo-threonine were similar to the respective glycine binary complexes. The structure of the ternary complex of F351G bsSHMT with glycine and FTHF (5-formyl THF) showed that the monoglutamate side chain of FTHF is ordered in both the subunits of the asymmetric unit, unlike in the wild-type bsSHMT. The present studies demonstrate that the residues Asn(341) and Tyr(60) are pivotal for the binding of THF/FTHF, whereas Phe(351) is responsible for the asymmetric binding of FTHF in the two subunits of the dimer.

Synthesis, structure and spectroscopic studies on hydroxo-bridged heterotrinuclear complexes of cobalt(m) with ethane-l,2-diamine and ammonia as terminal ligands

Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have envelope conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

High-Pressure Low-Temperature Locknut Cell For Both Electron-Paramagnetic-Res And Nmr-Studies To 10 Kilobars And 77-K

A locked high-pressure cell with working pressure range up to 10 kbars suitable for low-temperature studies to 77 K has been described. It can be used for both EPR and NMR studies of single crystals (and other solid samples). The high-pressure seal and all other aspects of the cell remain the same for either application. Only a change of the bottom plug is required for a switch from a nuclear-magnetic-resonance (NMR) to an electron-paramagnetic-resonance (EPR) experiment. Details of the procedure for the calibration of pressure inside the cell at various temperatures are discussed. The performance of the cell in EPR (Cr3+ion) and NMR (27Al nucleus) studies is reported.

Conformational analysis of small disulfide loops. Spectroscopic and theoretical studies on a synthetic cyclic tetrapeptide containing cystine

The conformational analysis of the synthetic peptide Boc-Cys-Pro-Val-Cys-NHMe has been carried out, as a model for small disulfide loops, in biologically active polypeptides. 'H NMR studies (270 MHz) establish that the Val(3) and Cys(4) NH groups are solvent shielded, while 13C studies establish an all-trans peptide backbone. Circular dichroism and Raman spectroscopy provide evidence for a right-handed twist of the disulfide bond. Analysis of the vicinal (JaB)c oupling constants for the two Cys residues establishes that XI - *60° for Cys(4), while some flexibility is suggested at Cys( 1). Conformational energy calculations, imposing intramolecular hydrogen bonding constraints, favor a P-turn (type I) structure with Pro(2)-Va1(3) as the corner residues. Theoretical and spectroscopic results are consistent with the presence of a transannular 4 - 1 hydrogen bond between Cys( 1) CO and Cys(4) NH groups, with the Val NH being sterically shielded from the solvent environment.

A unified approach to the gauging of space-time and internal symmetries

The properties of the manifold of a Lie groupG, fibered by the cosets of a sub-groupH, are exploited to obtain a geometrical description of gauge theories in space-timeG/H. Gauge potentials and matter fields are pullbacks of equivariant fields onG. Our concept of a connection is more restricted than that in the similar scheme of Ne'eman and Regge, so that its degrees of freedom are just those of a set of gauge potentials forG, onG/H, with no redundant components. The ldquotranslationalrdquo gauge potentials give rise in a natural way to a nonsingular tetrad onG/H. The underlying groupG to be gauged is the groupG of left translations on the manifoldG and is associated with a ldquotrivialrdquo connection, namely the Maurer-Cartan form. Gauge transformations are all those diffeomorphisms onG that preserve the fiber-bundle structure.

Thermochemical and kinetic studies on the effects of cobalt salicylate on the oxidative degradation of polystyrene

The effect of cobalt salicylate on the oxidative degradation and ignition of polystyrene has been studied. It was found that cobalt salicylate sensitizes both the degradation and ignition of polystyrene by facilitating electron-transfer processes in the propagation step. From thermochemical and kinetic studies it was found that the cobalt ion, owing to its ability to exist in variable valence states, promotes electron transfer in the propagation step of polymer degradation, increasing the rate of propagation and consequently the overall rate. Using solid-phase thermal ignition theory, an attempt has been made to explain the sensitization of ignition by the cobalt ion.

Crystallographic and modelling studies on Mycobacterium tuberculosis RuvA: Additional role of RuvB-binding domain and inter species variability

RuvA, along with RuvB, is involved in branch migration of heteroduplex DNA in homologous recombination. The structures of three new crystal forms of RuvA from Mycobacterium tuberculosis (MtRuvA) have been determined. The RuvB-binding domain is cleaved off in one of them. Detailed models of the complexes of octameric RuvA from different species with the Holliday junction have also been constructed. A thorough examination of the structures presented here and those reported earlier brings to light the hitherto unappreciated role of the RuvB-binding domain in determining inter-domain orientation and oligomerization. These structures also permit an exploration of the interspecies variability of structural features such as oligomerization and the conformation of the loop that carries the acidic pin, in terms of amino acid substitutions. These models emphasize the additional role of the RuvB-binding domain in Holliday junction binding. This role along with its role in oligomerization could have important biological implications.