Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions

The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the ""complex"" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Protein-polysaccharide viscoelastic matrices: synergic effects of amylose on lysozyme physical gelation in aqueous dimethylsulfoxide

A synergic effect of amylose on rheological characteristics of lysozyme physical gels evolved out of dimethylsulfoxide-water was verified and analyzed. The dynamics of the gels were experimentally approached by oscillatory rheology. The synergic effect was characterized by a decrease in the threshold DMSO volume fraction required for lysozyme gelation, and by a significant strengthening of the gel structure at over-critical solvent and protein concentrations. Drastic changes in the relaxation and creep curve patterns for systems in the presence of amylose were verified. Complex viscosity dependence on temperature was found to conform to an Arrhenius-like equation, allowing the determination of an activation energy term (Ea, apparent) for discrimination of gel rigidity. A dilatant effect was found to be induced by temperature on the flow behavior of lysozyme dispersions in DMSO-H(2)O in sub-critical conditions for gelation, which was greatly intensified by the presence of amylose in the samples. That transition was interpreted as reflecting a change from a predominant colloidal flow regime, where globular components are the prevailing structural elements, to a mainly fibrillar, polymeric flow behavior.

On the stabilization of conducting pernigraniline salt by the synthesis and oxidation of polyaniline in hydrophobic ionic liquids

The electrochemical polymerization of aniline in a hydrophobic room-temperature ionic liquid and the spectroelectrochemical characterization of the formed film are presented. The polymerization occurs without the presence of acid in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMITFSI), leading to a very stable electroactive material where no degradation was observed even at high applied potentials. Both in situ UV-Vis and Raman spectroscopic studies provided evidence for the stabilization of pernigraniline salt at high oxidation potentials and that this polyaniline state is the conducting form, as was corroborated by in situ resistance measurements. These data are indicative that low conductivity is not an intrinsic property of pernigraniline salt and this point must be reconsidered.

Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies

Oxidation of ethanol on ruthenium-modified Pt(775) and Pt(332) stepped electrodes has been studied using electrochemical and FTIR techniques. It has been found that the oxidation of ethanol on these electrodes takes place preferentially on the step sites yielding CO(2) as the major final product. The cleavage of the C-C bond, which is the required step to yield CO(2), occurs only on this type of site. The presence of low ruthenium coverages on the step sites promotes the complete oxidation of ethanol since it facilitates the oxidation of CO formed on the step from the cleavage of the C-C bond. However, high ruthenium coverages have an important inhibiting effect since the adatoms block the step sites, which are required for the cleavage of the C-C bond. Under these conditions, the oxidation current diminishes and the major product in the oxidation process is acetic acid, which is the product formed preferentially on the (111) terrace sites.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Self-organized distribution of periodicity and chaos in an electrochemical oscillator

We report a detailed numerical investigation of a prototype electrochemical oscillator, in terms of high-resolution phase diagrams for an experimentally relevant section of the control (parameter) space. The prototype model consists of a set of three autonomous ordinary differential equations which captures the general features of electrochemical oscillators characterized by a partially hidden negative differential resistance in an N-shaped current-voltage stationary curve. By computing Lyapunov exponents, we provide a detailed discrimination between chaotic and periodic phases of the electrochemical oscillator. Such phases reveal the existence of an intricate structure of domains of periodicity self-organized into a chaotic background. Shrimp-like periodic regions previously observed in other discrete and continuous systems were also observed here, which corroborate the universal nature of the occurrence of such structures. In addition, we have also found a structured period distribution within the order region. Finally we discuss the possible experimental realization of comparable phase diagrams.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Influence of gelation time on the morphological and physico-chemical properties of the sol-gel entrapped lipase

Different gelation times (4, 18, 24 and 48 h) were used for the preparation of silica sol-gel supports and encapsulated Candida rugosa lipase using tetraethoxysilane (TEOS) as precursor. The hydrophobic matrices and immobilized lipases produced were characterized with regard to pore volume and size by nitrogen adsorption (BJH method), weight loss upon heating (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), chemical composition (FTIR) and percentage of hydrolysis (POH%) of olive oil. These structural parameters were found to change with the gelation time, but no direct relation was found between the percentage of oil hydrolysis (POH%) and the gelation time. The best combination of high thermal stability and high POH% (99.5%) occurred for encapsulated lipase produced with 24 h gelation time. (C) 2007 Elsevier B.V. All rights reserved.

Preparation and characterization of Mo/W bimetallic carbides by using different synthesis methods

Molybdenum and tungsten bimetallic oxides were synthetized according to the following methods: Pechini, coprecipitation and solid state reaction (SSR). After the characterization, those solids were carbureted at programmed temperature. The carburation process was monitored by checking the consumption of carburant hydrocarbon and CO produced. The monitoring process permits to avoid or to diminish the formation of pirolytic carbon.

Rapid solidification and phase stability evaluation of Ti-Si-B alloys

Ti-rich Ti-Si-B alloys can be considered for structural applications at high temperatures (max. 700 degrees C), however, phase equilibria data is reported only for T = 1250 degrees C. Thus, in this work the phase stability of this system has been evaluated at 700 degrees C. In order to attain equilibrium conditions in shorter time, rapid solidified samples have been prepared and carefully characterized. The microstructural characterization of the produced materials were based on X-ray diffraction (XRD), scanning electron microscopy (SEM-BSE), high resolution transmission electron microscopy (HRTEM), High Temperature X-ray diffraction with Synchrotron radiation (XRDSR) and Differential Scanning Calorimetry (DSC). Amorphous and amorphous with embedded nanocrystals have been observed after rapid solidification from specific alloy compositions. The values of the crystallization temperature (Tx) of the alloys were in the 509-647 degrees C temperature range. After Differential Scanning Calorimetry and High Temperature X-ray Diffraction with Synchrotron radiation, the alloys showed crystalline and basically formed by two or three of the following phases: alpha Ti, Ti(6)Si(2)B; Ti(5)Si(3); Ti(3)Si and TiB. It has been shown the stability of the Ti(3)Si and Ti(6)Si(2)B phases at 700 degrees C and the proposition of an isothermal section at this temperature. (C) 2011 Elsevier B.V. All rights reserved.

Immobilization and stabilization of microbial lipases by multipoint covalent attachment on aldehyde-resin affinity: Application of the biocatalysts in biodiesel synthesis

Microbial lipase preparations from Thermomyces lanuginosus (TLL) and Pseudomonas fluorescens (PFL) were immobilized by multipoint covalent attachment on Toyopearl AF-amino-650M resin and the most active and thermal stable derivatives used to catalyze the transesterificanon reaction of babassu and palm oils with ethanol in solvent-free media For this different activating agents mainly glutaraldehyde glycidol and epichlorohydrin were used and immobilization parameters were estimated based on the hydrolysis of olive oil emulsion and butyl butyrate synthesis ILL immobilized on glyoxyl-resin allowed obtaining derivatives with the highest hydrolytic activity (HA(der)) and thermal stability between 27 and 31 times more stable than the soluble lipase Although PFL derivatives were found to be less active and thermally stables similar formation of butyl butyrate concentrations were found for both ILL and PFL derivatives The highest conversion into biodiesel was found in the transesterification of palm oil catalyzed by both ILL and PFL glyoxyl-derivatives (c) 2010 Elsevier B V All rights reserved

Magnetization studies of binary and ternary Co-rich phases of the Co-Si-B system

CoB, CO(2)B, CoSi, Co(2)Si and CO(5)Si(2)B phases can be formed during heat-treatment of amorphous co-Si-B soft magnetic materials. Thus, it is important to determine their magnetic behavior as a function of applied field and temperature. In this study, polycrystalline single-phase samples of the above phases were produced via arc melting and heat-treatment under argon. The single-phase nature of the samples was confirmed via X-ray diffraction experiments. AC and DC magnetization measurements showed that Co(2)Si and CO(5)Si(2)B phases are paramagnetic. Minor amounts of either Co(2)Si or CoSi(2) in the CoSi-phase sample suggested a paramagnetic behavior of the CoSi-phase, however, it should be diamagnetic as shown in the literature. The diamagnetic behavior of the CoB phase was also confirmed. The paramagnetic behavior of CO(5)Si(2)B is for the first time reported. The magnetization results of the phase CO(2)B have a ferromagnetic signature already verified on previous NMR studies. A detailed set of magnetization measurements of this phase showed a change of the easy magnetization axis starting at 70K, with a temperature interval of about 13K at a very small field of 1 mT. As the strength of the field is increased the temperature interval is enlarged. The strength of field at which the magnetization saturates increases almost linearly as the temperature is increased above 70K. The room temperature total magnetostriction of the CO(2)B phase was determined to be 8 ppm at a field of 1T. (C) 2010 Elsevier B.V. All rights reserved.

Interesterification of milkfat and soybean oil blends catalyzed by immobilized Rhizopus oryzae lipase

Milkfat (MF)/soybean oil (SBO) blends ranging from 50% to 100% of milkfat (w/w) were enzymatically interesterified with a sn-1,3 specific lipase from Rhizopus oryzae immobilized on polysiloxane-polyvinyl alcohol matrix, in a solvent free medium. Interesterification progress was monitored by following the changes in the relative proportions of 50-carbon triacylglycerols (TAGS) to 44-carbon TAGs (50/44 ratio) in the reaction. The starting materials and products were also analyzed in terms of consistency measured in a texturometer. All reactions gave interesterified (IE) products with lower consistency than non-interesterified (NIE) MF:SBO blends and interesterification degree varied from 0.54 to 2.60 in 48 h reaction. The highest interesterification degree was achieved for 65:35 MF:SBO blends, which gave 76% reduction in the consistency. These results showed the potential of the immobilized lipase to change the TAGs profile of the MF:SBO blend allowing to obtain cold-spreadable milkfat. (C) 2010 Elsevier B.V. All rights reserved.

Adsorption kinetic, thermodynamic and desorption studies of phosphate onto hydrous niobium oxide prepared by reverse microemulsion method

A type of Nb(2)O(5)center dot 3H(2)O was synthesized and its phosphate removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The phosphate adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 18.36 mg-Pg(-1). The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. A phosphate desorbability of approximately 68% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical attraction. Due to its high adsorption capacity, this type of hydrous niobium oxide has the potential for application to control phosphorus pollution.