Identification and thermodynamic characterization of molten globule states of periplasmic binding proteins

Molten globule-like intermediates have been shown to occur during protein folding and are thought to be involved in protein translocation and membrane insertion. However, the determinants of molten globule stability and the extent of specific packing in molten globules is currently unclear. Using far- and near-UV CD and intrinsic and ANS fluorescence, we show that four periplasmic binding proteins (LBP, LIVBP, MBP, and RBP) form molten globules at acidic pH values ranging from 3.0 to 3.4. Only two of these (LBP and LIVBP) have similar sequences, but all four proteins adopt similar three-dimensional structures. We found that each of the four molten globules binds to its corresponding ligand without conversion to the native state. Ligand binding affinity measured by isothermal titration calorimetry for the molten globule state of LIVBP was found to be comparable to that of the corresponding native state, whereas for LBP, MBP, and RBP, the molten globules bound ligand with approximately 5-30-fold lower affinity than the corresponding native states. All four molten globule states exhibited cooperative thermal unfolding assayed by DSC. Estimated values of Delta C-p of unfolding show that these molten globule states contain 28-67% of buried surface area relative to the native states. The data suggest that molten globules of these periplasmic binding proteins retain a considerable degree of long range order. The ability of these sequentially unrelated proteins to form highly ordered molten globules may be related to their large size as well as an intrinsic property of periplasmic binding protein folds.

Photocatalytic degradation of methyl methacrylate copolymers

The photolytic and photocatalytic degradation of the copolymers poly(methyl methacrylate-co-butyl methacrylate) (MMA–BMA), poly(methyl methacrylate-co-ethyl acrylate) (MMA–EA) and poly(methyl methacrylate-co-methacrylic acid) (MMA–MAA) have been carried out in solution in the presence of solution combustion synthesized TiO2 (CS TiO2) and commercial Degussa P-25 TiO2 (DP 25). The degradation rates of the copolymers were compared with the respective homopolymers. The copolymers and the homopolymers degraded randomly along the chain. The degradation rate was determined using continuous distribution kinetics. For all the polymers, CS TiO2 exhibited superior photo-activity compared to the uncatalysed and DP 25 systems, owing to its high surface hydroxyl content and high specific surface area. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the Fourier transform-infrared (FT-IR) spectra of the copolymers indicated that the degradation rate follows the order MMA–MAA > MMA–EA > MMA–BMA. The same order is observed for the rate coefficients of photocatalytic degradation. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. In degradation by pyrolysis, it was observed that MMA–BMA was the least stable followed by MMA–EA and MMA–MAA. The observed contrast in the order of thermal stability compared to the photo-stability of these copolymers was attributed to the two different mechanisms governing the scission of the polymer and the evolution of the products.

Surfactant stabilized nanopetals morphology of α-MnO2 prepared by microemulsion method

α-Manganese dioxide is synthesized in a microemulsion medium by a redox reaction between KMnO4 and MnSO4 in presence of sodium dodecyl sulphate as a surface active agent. The morphology of MnO2 resembles nanopetals, which are spread parallel to the field. The material is further characterized by powder X-ray diffraction, energy dispersive analysis of X-ray, and Brunauer–Emmett–Teller surface area. Supercapacitance property of α-MnO2 nanopetals is studied by cyclic voltammetry and galvanostatic charge–discharge cycling. High values of specific capacitance are obtained.

Synthesis and characterization of nano-MnO2 for electrochemical supercapacitor studies

Nanostructured MnO2 was synthesized at ambient condition by reduction of potassium permanganate with aniline. Powder X-ray diffraction, thermal analysis (thermogravimetric and differential thermal analysis), Brunauer-Emmett-Teller surface area, and infrared spectroscopy studies were carried out for physical and chemical characterization. The as-prepared MnO2 was amorphous and contained particles of 5-10 nm diameter. Upon annealing at temperatures >400°C, the amorphous MnO2 attained crystalline α-phase with a concomitant change in morphology. A gradual conversion of nanoparticles to nanorods is evident from scanning electron microscopy and transmission electron microscopy (TEM) studies. High-resolution TEM images suggested that nanoparticles and nanorods grow in different crystallographic planes. Capacitance behavior was studied by cyclic voltammetry and galvanostatic charge-discharge cycling in a potential range from -0.2 to 1.0 V vs SCE in 0.1 M sodium sulfate solution. Specific capacitance of about 250 F g-1 was obtained at a current density of 0.5 mA cm-2(0.8 A g-1).

Graphene Analogues of BN: Novel Synthesis and Properties

Enthused by the fascinating properties of graphene, we have prepared graphene analogues of BN by a chemical method with a control on the number of layers. The method involves the reaction of boric acid with urea, wherein the relative proportions of the two have been varied over a wide range. Synthesis with a high proportion of urea yields a product with a majority of 1-4 layers. The surface area of BN increases progressively with the decreasing number of layers, and the high surface area BN exhibits high CO, adsorption, but negligible H, adsorption. Few-layer BN has been solubilized by interaction with Lewis bases. We have used first-principles simulations to determine structure, phonon dispersion, and elastic properties of BN with planar honeycomb lattice-based n-layer forms. We find that the mechanical stability of BN with respect to out-of-plane deformation is quite different from that of graphene, as evident in the dispersion of their flexural modes. BN is softer than graphene and exhibits signatures of long-range ionic interactions in its optical phonons. Finally, structures with different stacking sequences of BN have comparable energies, suggesting relative abundance of slip faults, stacking faults, and structural inhomogeneities in multilayer BN.

Conformations of disulfide bridges in proteins

The conformational characteristics of disulfide bridges in proteins have been analyzed using a dataset of 22 protein structures, available at a resolution of 2.0 Å, containing a total of 72 disulfide crosslinks. The parameters used in the analysis include (φ, Ψ) values at Cys residues, bridge dihedral angles χss, χ1i, χ1j, χ2i and χ2j the distances Cαi-Cαj and Cβi-Cβj between the Cα and Cβ atoms of Cys(i) and Cys(j). Eight families of bridge conformations with three or more occurrences have been identified on the basis of these stereochemical parameters. The most populated family corresponds to the "left handed spiral" identified earlier by Richardson ((1981) Adv. Protein Chem. 34, 167–330). Disulfide bridging across antiparallel extended strands is observed in α-lytic protease, crambin, and β-trypsin and this structure is shown to be very similar to those obtained in small cystine peptides. Solvent accessible surface area calculations show that the overwhelming majority of disulfide bridges are inaccessible to solvent.

Photocatalytic degradation of dyes over combustion synthesized Ce1-xFexVO4

Fe-substituted CeVO4 was synthesized by the solution combustion technique and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectroscopy, transmission electron microscopy and BET surface area analyzer. These compounds crystallized in tetragonal zircon structure with Fe substituted in ionic state for Ce3+ ions. The degradation of anionic and cationic dyes was studied over Fe-substituted CeVO4 compounds. The compounds showed high photocatalytic activity towards dye degradation. The effect of amount of substitution was studied by varying the Fe substitution from 1 to 10%. The rates decreased with increasing substitution of Fe in CeVO4 and 1% Fe substituted CeVO4 showed the highest photocatalytic activity. (C) 2010 Elsevier B.V. All rights reserved.

Effect of fuel on the formation structure, transport and magnetic properties of LaMnO3+nanopowders

Single-step low-temperature solution combustion (LCS) synthesis was adopted for the preparation of LaMnO3+ (LM) nanopowders. The powders were well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS),surface area and Fourier transform infrared spectroscopy (FTIR). The PXRD of as-formed LM showed a cubic phase but, upon calcination (900degrees C, 6 h), it transformed into a rhombohedral phase. The effect of fuel on the formation of LM was examined, and its structure and magnetoresistance properties were investigated. Magnetoresistance (MR) measurements on LM were carried out at 0, 1, 4 and 7 T between 300 and 10 K. LM (fuel-to-oxidizer ratio; = 1) showed an MR of 17% at 1 T, whereas, for 4 and 7 T, it exhibited an MR of 45 and 55%, respectively, near the TM-I. Metallic resistivity data below TM-I showed that the double exchange interaction played a major role in this compound. It was interesting to observe that the sample calcined at 1200 degrees C for 3 h exhibited insulator behavior.

Mechanism of crystal structure transformations. Part 3. - Factors affecting the anatase-rutile transformation

The particle size and crystallite size of anatase increase markedly in the region of the crystal structure transformation. The unit cell of anatase seems to expand prior to the transformation to rutile. This expansion has been attributed to a displacive transformation of the type defined by Buerger. Smaller particle size and larger surface area seem to favour the transformation. The kinetics of the transformation of anatase prepared by the hydrolysis of titanium sulphate have been studied at different temperatures and are found to be considerably different from the kinetics of the transformation of pure anatase. The transformation becomes immeasurably slow below ∼695 ± 10°C compared to ∼610°C for pure anatase. An induction period is observed in the transformation of anatase obtained from sulphate hydrolysis and the duration decreases with increase in temperature. The activation energy is ∼120 kcal/mole, a value higher than that for the pure anatase-rutile transformation. The results have been interpreted in terms of the relative rates of nucleation and propagation processes. The activation energy for the nucleation process seems to be much larger than for the propagation process. The kinetics of the transformation of anatase samples doped with different amounts of sulphate ion impurity have also been studied and the transformation is found to be progressively decelerated with increase in the impurity concentration. The energy of activation for the transformation appears to increase progressively with increase in impurity concentration.

Single-Shot Preparation of Crystalline Nanoplate LiFePO4 by a Simple Polyol Route

Nanoplate LiFePO4 is synthesized by a polyol route starting from only two reactants, namely, FePO4 and LiOH. The crystalline compound forms by refluxing a tetraethylene glycol solution consisting of FePO4 and LiOH at 335 degrees C without further heating of the reaction product.The nanoplates have average dimensions of 30 nm width and 160 nm length, as measured from transmission electron microscopy micrographs.The surface area of the LiFePO4 sample is 38 m(2) g(-1). Also, the sample is porous with a broadly distributed pore around 50 nm. The electrodes fabricated out of the nanoplate of LiFePO4 exhibit a high electrochemical activity. Discharge capacity values measured are 160 and 100 mAh g(-1) at 0.15C and 3.45C, respectively. A stable capacity of about 155 mAh g(-1) is measured at 0.2C over a 50 charge-discharge cycle. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3425730] All rights reserved.

A Durable PEFC with Carbon-Supported Pt-TiO2 Cathode: A Cause and Effect Study

Durability is central to the commercialization of polymer electrolyte fuel cells (PEFCs). The incorporation of TiO2 with platinum (Pt) ameliorates both the stability and catalytic activity of cathodes in relation to pristine Pt cathodes currently being used in PEFCs. PEFC cathodes comprising carbon-supported Pt-TiO2 (Pt-TiO2/C) exhibit higher durability in relation to Pt/C cathodes as evidenced by cell polarization, impedance, and cyclic voltammetry data. The degradation in performance of the Pt-TiO2/C cathodes is 10% after 5000 test cycles as against 28% for Pt/C cathodes. These data are in conformity with the electrochemical surface area and impedance values. Pt-TiO2/C cathodes can withstand even 10,000 test cycles with nominal effect on their performance. X-ray diffraction, transmission electron microscope, and cross-sectional field-emission-scanning electron microscope studies on the catalytic electrodes reflect that incorporating TiO2 with Pt helps in mitigating the aggregation of Pt particles and protects the Nafion membrane against peroxide radicals formed during the cathodic reduction of oxygen. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3421970] All rights reserved.

High Rate Capability of Porous LiNi1/3Co1/3Mn1/3O2 Synthesized by Polymer Template Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural with LiCoO2, is considered as a potential cathode material for Li-ion batteries. Submicrometer sized porous particles are useful for high discharge rates. The present work involves a synthesis of submicrometer sized porous particles of LiNi1/3Co1/3Mn1/3O2 using a triblock copolymer as a soft template. The precursor obtained from the reaction is heated at different temperatures between 600 and 900 degrees C for 6 h to get the final product samples. The compound attains increased crystallinity with an increase in the temperature of preparation. However, there is a decrease in the surface area and also in the porosity of the sample. Nevertheless, the LiNi1/3Co1/3Mn1/3O2 sample prepared at 900 degrees C exhibits a high rate capability and stable capacity retention on cycling. The electrochemical performance of LiNi1/3Co1/3Mn1/3O2 prepared in the absence of the polymer template is inferior to that of the sample prepared in the presence of the polymer template. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3364944] All rights reserved.

Solution-Combustion Synthesized Nanocrystalline Li4Ti5O12 As High-Rate Performance Li-Ion Battery Anode

Nanocrystalline Li4Ti5O12 (LTO) crystallizing in cubic spinel-phase has been synthesized by single-step-solution-combustion method in less than one minute. LTO particles thus synthesized are flaky and highly porous in nature with a surface area of 12 m(2)/g. Transmission electron micrographs indicate the primary particles to be agglomerated crystallites of varying size between 20 and 50 nm with a 3-dimensional interconnected porous network. During their galvanostatic charge-discharge at varying rates, LTO electrodes yield a capacity value close to the theoretical value of 175 mA h/g at C/2 rate. The electrodes also exhibit promising capacity retention with little capacity loss over 100 cycles at varying discharge rates together with attractive discharge-rate capabilities yielding capacity values of 140 mA h/g and 70 mA h/g at 10 and 100 C discharge rates, respectively. The ameliorated electrode-performance is ascribed to nano and highly porous morphology of the electrodes that provide short diffusion-paths for Li in conjunction with electrolyte percolation through the electrode pores ensuring a high flux of Li.

Vapour phase synthesis of salol over solid acids via transesterification

The transesterification of methyl salicylate with phenol has been studied in vapour phase over solid acid catalysts such as ZrO2, MoO3 and SO42- or Mo(VI) ions modified zirconia. The catalytic materials were prepared and characterized for their total surface acidity, BET surface area and powder XRD patterns. The effect of mole-ratio of the reactants, catalyst bed temperature, catalyst weight, flow-rate of reactants, WHSV and time-on-stream on the conversion (%) of phenol and selectivity (%) of salol has been investigated. A good yield (up to 70%) of salol with 90% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 degrees C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of SO42- or Mo(VI) ions. The effect of poisoning of acid sites of SO42- or Mo(VI) ions modified zirconia on total surface acidity, powder XRD phases and catalytic activity was also studied. Possible reaction mechanisms for the formation of salol and diphenyl ether over acid sites are proposed.

Rare-earth chromium citrates as precursors for rare-earth chromites: lanthanum biscitrato chromium(III) dihydrate, La[Cr(C6H5O7)2]·2H

The thermal decomposition of lanthanum biscitrato chromium(III) dihydrate has been studied in static air and dynamic argon atmospheres. The complex decomposes in four steps: dehydration, decomposition of the citrate to an intermediate oxycarbonate, formation of LaCrO4(V) from oxycarbonate, and finally decomposition of LaCrO4(V) to LaCrO3. Formation of LaCrCrO4(V) requires the presence of oxygen The decomposition behaviour of a mechanical mixture of lanthanum citrate hydrate and chromium citrate hydrate was compared with that of the citrato complex. Both the starting material and the intermediates were characterized by X-ray diffraction, IR electronic and ESR spectroscopy, surface area and magnetic susceptibility measurements, as well as by chemical analysis. A scheme is proposed for the decomposition of lanthanum biscitrato chromium(III) dihydrate in air. LaCrO3 can be obtained at temperatures as low as 875 K by isothermal decomposition of the complex.