Disruption of the 2-methylcitric acid cycle and evaluation of poly-3-hydroxybutyrate-co-3-hydroxyvalerate biosynthesis suggest alternate catabolic pathways of propionate in Burkholderia sacchari

The objective of the present work was to evaluate the relevance of the 2-methylcitric acid cycle (2MCC) to the catabolism of propionate in Burkholderia sacchari. Two B. sacchari mutants unable to grow on propionate were obtained: one disrupted in acnM, and the other in acnM and prpC deleted. An operative 2MCC significantly reduces the bacterial ability to incorporate 3-hydroxyvalerate (3HV) into a biodegradable copolyester accumulated from carbohydrates plus propionate. The efficiency of the mutants in converting propionate to 3HV units (Y(3HV/prp)) increased from 0.09 g.g(-1) to 0.81-0.96 g.g(-1), indicating that acnM and prpC are both essential for growth on propionate. None of the mutations resulted in achievement of the maximum theoretical Y(3HV/prp) (1.35 g.g(-1)). When increasing concentrations of propionate were supplied, decreasing values of Y(3HV/prp) were observed. The results obtained corroborate the hypothesis of the presence of other propionate catabolic pathways in B. sacchari. The 2MCC would be the more operative pathway, but a second pathway, which remains to be elucidated, would assume more importance under propionate concentrations of 1 g.L(-1) or higher. The efficiency in converting propionate to 3HV units can be improved by decreasing the propionate concentrations, owing to the role of the 2MCC.

Ionization and Structural Changes of the DMPG Vesicle along Its Anomalous Gel-Fluid Phase Transition: A Study with Different Lipid Concentrations

Dispersions of saturated anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG) have been extensively studied regarding their peculiar thermostructural behavior. At low ionic strength, the gel-fluid transition is spread along nearly 17 degrees C, displaying several thermal events in the calorimetric profile that is quite different from the single sharp peak around 23 degrees C found for higher ionic strength DMPG dispersions. To investigate the role of charge in the bilayer transition, we carefully examine the temperature dependence of the electrical conductivity of DMPG dispersions at different concentrations, correlating the data with the corresponding differential scanning calorimetry (DSC) traces. Electrical conductivity together with electrophoretic mobility measurements allowed the calculation of the dependence of the degree of ionization of DMPG vesicles on lipid concentration and temperature. It was shown that there is a decrease in vesicle charge as the lipid concentration increases, which is probably correlated with the increase in the concentration of bulk Na(+). Apart from the known increase in the electrical conductivity along the DMPG temperature transition region, a sharp rise was observed at the bilayer pretransition for all lipid concentrations studied, possibly indicating that the beginning of the chain melting process is associated with an increase in bilayer ionization. It is confirmed here that the gel-fluid transition of DMPG at low ionic strength is accompanied by a huge increase in the dispersion viscosity. However, it is shown that this measured macroviscosity is distinct from the local viscosity felt by either charged ions or DMPG charged aggregates in measurements of electrical conductivity or electrophoretic mobility, Data presented here give support to the idea that DMPG vesicles, at low ionic strength, get more ionized along the temperature transition region and could be perforated and/or deformed vesicle structures.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Controlling the absorption and emission properties of polyparaphenylenevinylene films

In this work we used the conversion process of a precursor polymer into polyparaphenylenevinylene (PPV) at low temperatures in order to control the effective conjugation degree of spin-casted PPV films. The absorption and emission spectra of the films were studied by following a partial substitution of chloride counterions from poly(xylylidene tetrahydrothiophenium chloride) (PTHT), used as a precursor, by sodium acid dodecyl benzenesulfonate (DBS), added as a surfactant salt. Upon controlling the DBS amount and conversion temperature (T-c) of PTHT/DBS to PPV films, the band gap of PPV changed from 409 to 506 nm, and 505 to 532 nm, values obtained from absorbance and emission measurements, respectively. Based on these experimental data, we proposed a physical model which represents the chemical structure of PPV as a distribution of conjugated chain segments (like oligomers) alternated by non-conjugated segments (structural defects and/or from the precursor polymer). (C) 2008 Elsevier B.V. All rights reserved.

Immobilization of Poly(propylene imine) Dendrimer/Nickel Phtalocyanine as Nanostructured Multilayer Films To Be Used as Gate Membranes for SEGFET pH Sensors

We describe the assembly of layer-by-layer films based on the poly(propylene imine) dendrimer (PPID) generation 3 and nickel tetrasulfonated phthalocyanine (NiTsPc) for application as chemically sensitive membranes in sepal alive extended-gate field effect transistor (SEGFET) pH sensors PPID/NiTsPc films wet e adsorbed on quartz, glass. indium tin oxide. or gold (Au)-covered glass substrates Multilayer formation was monitored via UV-vis absorption upon following the increment in the Q-band intensity (615 nm) of NiTsPc The nanostructured membranes were very stable in a pH range of 4-10 and displayed a good sensitivity toward H(+), ca 30 mV/pH for PPID/N(1)TsPc films deposited on Au-covered substrates For films deposited on ITO, the sensitivity was ca 52 4 mV/pH. close to the expected theoretical value for ton-sensitive membranes. The use of chemically stable PPID/NiTsPc films as gate membranes in SEGFETs, as introduced here, may represent an alternative for the fabrication of nanostructured, porous platforms for enzyme immobilization to be used in enzymatic biosensors.

De-aggregation of polyfluorene derivative by blending with a series of poly(alkyl methacrylate)s with varying sidegroup sizes

A polyfluorene derivative of the PPV, poly(9,9`-n-dihexyl-2,7-fluorenedilvinylene-alt-1,4-phenylenevinylene), with a strong tendency to aggregation was blended with several members of a series composed by poly(alkyl methacrylate)s with the following substituents in the ester position: methyl, ethyl, isopropyl, isobutyl, n-butyl, and cyclohexyl. The de-aggregation effect in blends was studied by steady-state photoluminescence spectroscopy using several blend compositions. The efficiency of each dispersing phase was discussed in terms of the polymer miscibility, controlled by interaction parameters between the polyfluorene and every poly(alkyl methacrylate)s, here described using Hilde-brand solubility parameters. (c) 2009 Elsevier Ltd. All rights reserved.

Spectroscopic and structural studies of bis[isopropoxy(thiocarbonyl)]sulfide, [(CH(3))(2)CHOC(S)](2)S

Structural and conformational properties of the molecule bis[isopropoxy(thiocarbonyl)]sulfide, [(CH(3))(2)CHOC(S)](2)S, have been studied by vibrational spectroscopy (IR and Raman) and quantum chemical calculations (HF and B3LYP with 6-31+G* basis sets). The crystal and molecular structure of the title compound was determined by X-ray diffraction methods. It crystallizes in the monoclinic C2/c space group with a = 8.4007(4), b = 13.5936(5), c = 10.3648(5) angstrom, beta = 106.024(4)degrees and Z = 4 molecules per unit cell. The molecules are sited on a crystallographic twofold axis passing through the sulphide atom and arranged in layers perpendicular to the b-axis. The solid state IR and Raman spectra of the compound give no sign of any other rotamer. (C) 2009 Elsevier B.V. All rights reserved.

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd-PSS films were processed using the acid of poly(styrene sulfonate) - H-PSS and neodymium nitrate - Nd(NO(3))(3); the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV-Vis-NIR spectral region presents typical electronic transitions of Nd 3, ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N-O groups in the range of 1400-720 cm(-1), prove the permanence of Nd(NO(3))(x), with x = 1, 2 and/or 3. in the H-PSS matrix. UV-Vis site selective photoluminescence data indicate that the incorporation of Nd 31 introduces a blue shift in PSS emission (325-800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd(3+) reabsorption and energy transfer effects between the PSS matrix and Nd(3+) were also observed. The IR emission of Nd-PSS films at 1076 rim ((4)F(3/2) -> (4)I(11/2)) present constant efficiency, independent on Nd(3+) concentration. The Judd-Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd(3+). Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix. (C) 2008 Elsevier B.V. All rights reserved.

Absorption and emission properties of LBL PPV films deposited on ITO electrodes

In this work we studied the properties of absorption and emission line shape of layer-by-layer (LBL) poly(p-phenylene vinylene) (PPV) on indium-tin oxide (ITO) electrode. To minimize the PPV thermal conversion effects during the polymer processing, we used a less aggressive leaving group in the precursor polymer; minimizing electrode degradation. LBL ITO/PPV films showed the same absorption and emission line shape compared with LBL PPV films deposited on non-metallic substrates (glass). With this analysis we indirectly observe the decrease in the ITO degradation. Atomic force microscopy (AFM) technique was used to analyze quantitatively the microscopic morphology of the film surface. Results indicated that the substrate topology is not affected, to a large extent, by the use of dodecylbenzensulfonate (DBS) ion. (C) 2008 Elsevier B.V. All rights reserved.

On the pH dependence of electroactivity of poly(methylene blue) films

The electrochemical behavior of poly(methylene blue) on different electrodes has been investigated by electrochemical quartz crystal microbalance and in situ spectrophotometric measurements coupled to cyclic voltammetry. Polymeric films were obtained potentiodynamically and the charge transport mechanism was analyzed. The electrochemical results show that polymer electroactivity depends not only on pH but also on the substrate. Charge compensation changes with both pH and the size of the anions showing a transition in the pH range of polymer pKa. It was demonstrated by spectroelectrochemical experiments that the electroactivity of the film depends on the radical/radical cation equilibrium. The potentials where the most electroactive species are formed have been determined. (C) 2009 Elsevier Ltd. All rights reserved.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

Crosslinking of Poly(N-vinyl-2-pyrrolidone) in the Coating of Cotton Yarn

Coating of cotton yarn is employed in the textile industry to increase the mechanical resistance of the yarns and resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study is to investigate the usage of a synthetic hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (PVP), to coat 100% cotton textile yarn, aiming to give the yarn a temporary mechanical resistance. For the improvement of the mechanical resistance of the yarn, the following crosslinking processes of PVP were investigated: UV-C (ultraviolet) radiation, the Fenton and photo-Fenton reactions, and sensitized UV-C radiation. The influence of each crosslinking process was determined through tensile testing of the coated yarns. The results indicated that the best crosslinking process employed was UV-C radiation; increasing the mechanical resistance of the yarn up to 44% if compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. POLYM. ENG. SCI., 51:445-453, 2011. (C) 2010 Society of Plastics Engineers

Effect of adding CaO to ZrO(2) support on nickel catalyst activity in dry reforming of methane

Nickel catalysts with a load of 5 wt% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4, 8 and 14 mol% CaO, were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and impedance spectroscopy (IS) and tested in the carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of CaO-ZrO(2) solid solutions. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the support composition. The electrical properties of the support have a proportional effect on the catalytic activities. Catalytic tests were done at 800 degrees C for 6 h and the composition of the gaseous products and the catalytic conversion depended on the CaO-ZrO(2) solid solution composition and its influence on supported NiO species. A direct relation was found between the variation in the electrical conductivity of the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2009 Elsevier B.V. All rights reserved.

Effect of polyol excess on the electrical property of vegetable-polyurethane film

Freestanding castor oil-based polyurethane (PU) film was obtained using spin-coating method. The effect of polyol content was analysed by means of thermally stimulated depolarisation current and AC dielectric measurements techniques. Two relaxation peaks were observed in the temperature range of -40 to 60 degrees C for PU with different polyol contents. The presence of polyol excess provides a shift to lower temperature of the a relaxation and the decrease in the activation energy of the transition in this region might be attributed to the plasticising effect of the polyol. The peak at higher temperature is due to the Maxwell-Wagner-Sillars relaxation, which also shifts in the low temperature direction as the polyol content is increased.

Thioxanthone Sensitized Photodegradation of Poly(alkyl methacrylate) Films

The thioxanthone-sensitized photodegradation of poly(alkyl methacrylate) films [alkyl = methyl, ethyl, butyl, and hexyl] was studied using near UV-vis light. The photooxidation process continued even after the total consumption of the sensitizer, possibly due to the excitation of the ketyl groups formed during the first stages of the process. The rate of oxidation, as well as the formation of hydroxy, peroxy, and ketyl groups was faster for polymers with larger ester groups. The decrease of the molecular weight of the degradated polymers was also larger for the hexyl substituted polymer. The side-chain size effect was attributed to the larger amount of secondary hydrogens available for abstraction by the triplet state of thioxanthone, present in the larger ester groups. The lower glass transition temperature of the hexyl substituted polymer allows a better diffusion of oxygen to the deeper layers of the films that also contributes to the faster photodegradation rate. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1283-1288, 2010