Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations

In this study we address the problem of the response of a (electro)chemical oscillator towards chemical perturbations of different magnitudes. The chemical perturbation was achieved by addition of distinct amounts of trifluoromethanesulfonate (TFMSA), a rather stable and non-specifically adsorbing anion, and the system under investigation was the methanol electro-oxidation reaction under both stationary and oscillatory regimes. Increasing the anion concentration resulted in a decrease in the reaction rates of methanol oxidation and a general decrease in the parameter window where oscillations occurred. Furthermore, the addition of TFMSA was found to decrease the induction period and the total duration of oscillations. The mechanism underlying these observations was derived mathematically and revealed that inhibition in the methanol oxidation through blockage of active sites was found to further accelerate the intrinsic non-stationarity of the unperturbed system. Altogether, the presented results are among the few concerning the experimental assessment of the sensitiveness of an oscillator towards chemical perturbations. The universal nature of the complex chemical oscillator investigated here might be used for reference when studying the dynamics of other less accessible perturbed networks of (bio)chemical reactions.

New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination

Crown ethers have the ability of solubilizing inorganic salts in apolar solvents and to promote chemical reactions by phase-transfer catalysis. However, details on how crown ethers catalyze ionic S(N)2 reactions and control selectivity are not well understood. In this work, we have used high level theoretical calculations to shed light on the details of phase-transfer catalysis mechanism of KF reaction with alkyl halides promoted by 18-crown-6. A complete analysis of the of the model reaction between KF(18-crown-6) and ethyl bromide reveals that the calculations can accurately predict the product ratio and the overall kinetics. Our results point out the importance of the K* ion and of the crown ether ring in determining product selectivity. While the K* ion favors the S(N)2 over the E2 anti pathway, the crown ether ring favors the S(N)2 over E2 syn route. The combination effects lead to a predicted 94% for the S(N)2 pathway in excellent agreement with the experimental value of 92%. A detailed analysis of the overall mechanism of the reaction under phase-transfer conditions also reveals that the KBr product generated in the nucleophilic fluorination acts as an inhibitor of the 18-crown-6 catalyst and it is responsible for the observed slow reaction rate. (C) 2012 Elsevier B.V. All rights reserved.

Period adding cascades: Experiment and modeling in air bubbling

Period adding cascades have been observed experimentally/numerically in the dynamics of neurons and pancreatic cells, lasers, electric circuits, chemical reactions, oceanic internal waves, and also in air bubbling. We show that the period adding cascades appearing in bubbling from a nozzle submerged in a viscous liquid can be reproduced by a simple model, based on some hydrodynamical principles, dealing with the time evolution of two variables, bubble position and pressure of the air chamber, through a system of differential equations with a rule of detachment based on force balance. The model further reduces to an iterating one-dimensional map giving the pressures at the detachments, where time between bubbles come out as an observable of the dynamics. The model has not only good agreement with experimental data, but is also able to predict the influence of the main parameters involved, like the length of the hose connecting the air supplier with the needle, the needle radius and the needle length. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3695345]

Enzyme Microheterogeneous Hydration and Stabilization in Supercritical Carbon Dioxide

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Compact and autonomous multiwavelength microanalyzer for in-line and in situ colorimetric determinations

Nowadays, the attainment of microsystems that integrate most of the stages involved in an analytical process has raised an enormous interest in several research fields. This approach provides experimental set-ups of increased robustness and reliability, which simplify their application to in-line and continuous biomedical and environmental monitoring. In this work, a novel, compact and autonomous microanalyzer aimed at multiwavelength colorimetric determinations is presented. It integrates the microfluidics (a three-dimensional mixer and a 25 mm length "Z-shape" optical flow-cell), a highly versatile multiwavelength optical detection system and the associated electronics for signal processing and drive, all in the same device. The flexibility provided by its design allows the microanalyzer to be operated either in single fixed mode to provide a dedicated photometer or in multiple wavelength mode to obtain discrete pseudospectra. To increase its reliability, automate its operation and allow it to work under unattended conditions, a multicommutation sub-system was developed and integrated with the experimental set-up. The device was initially evaluated in the absence of chemical reactions using four acidochromic dyes and later applied to determine some key environmental parameters such as phenol index, chromium(VI) and nitrite ions. Results were comparable with those obtained with commercial instrumentation and allowed to demonstrate the versatility of the proposed microanalyzer as an autonomous and portable device able to be applied to other analytical methodologies based on colorimetric determinations.

Self-similarities of periodic structures for a discrete model of a two-gene system

We report self-similar properties of periodic structures remarkably organized in the two-parameter space for a two-gene system, described by two-dimensional symmetric map. The map consists of difference equations derived from the chemical reactions for gene expression and regulation. We characterize the system by using Lyapunov exponents and isoperiodic diagrams identifying periodic windows, denominated Arnold tongues and shrimp-shaped structures. Period-adding sequences are observed for both periodic windows. We also identify Fibonacci-type series and Golden ratio for Arnold tongues, and period multiple-of-three windows for shrimps. (C) 2012 Elsevier B.V. All rights reserved.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Selectivity and Mechanisms Driven by Reaction Dynamics: The Case of the Gas-Phase OH-+CH3ONO2 Reaction

Well-established statistical approaches such as transition-state theory based on high-level calculated potential energy profiles are unable to account for the selectivity observed in the gas-phase OH- + CH3ONO2 reaction. This reaction can undergo bimolecular nucleophilic displacement at either the carbon center (S(N)2@C) or the nitrogen center (S(N)2@N) as well as a proton abstraction followed by dissociation (E(CO)2) pathway. Direct dynamics simulations yield an S(N)2:E(CO)2 product ratio in close agreement with experiment and show that the lack of reactivity at the nitrogen atom is due to the highly negative electrostatic potential generated by the oxygen atoms in the ONO2 group that scatters the incoming OH-. In addition to these dynamical effects, the nonstatistical behavior of these reactions is attributed to the absence of equilibrated reactant complexes and to the large number of recrossings, which might be present in several ion-molecule gas-phase reactions.

Moving from surfactant-stabilized aqueous rhodium (0) colloidal suspension to heterogeneous magnetite-supported rhodium nanocatalysts: Synthesis, characterization and catalytic performance in hydrogenation reactions

Wet impregnation of pre-synthesized surfactant-stabilized aqueous rhodium (0) colloidal suspension on silica was employed in order to prepare supported Rh-0 nanoparticles of well-defined composition, morphology and size. A magnetic core-shell support of silica (Fe(3)O4@SiO2) was used to increase the handling properties of the obtained nanoheterogeneous catalyst. The nanocomposite catalyst Fe3O4@SiO2-Rh-0 NPs was highly active in the solventless hydrogenation of model olefins and aromatic substrates under mild conditions with turnover frequencies up to 143,000 h(-1). The catalyst was characterized by various transmission electron microscopy techniques showing well-dispersed rhodium nanoparticles (similar to 3 nm) mainly located at the periphery of the silica coating. The heterogeneous magnetite-supported nanocatalyst was investigated in the hydrogenation of cyclohexene and compared to the previous surfactant-stabilized aqueous Rh-0 colloidal suspension and various silica-supported Rh-0 nanoparticles. Finally, the composite catalyst could be reused in several runs after magnetic separation. (C) 2011 Elsevier B. V. All rights reserved.

The role of Ce(III) in BZ oscillating reactions

Herein we present results on the oscillatory dynamics in the bromate-oxalic acid-acetone-Ce(III)/Ce(IV) system in batch and also in a CSTR. We show that Ce(III) is the necessary reactant to allow the emergence of oscillations. In batch, oscillations occur with Ce(III) and also with Ce(IV), but no induction period is observed with Ce(III). In a CSTR, no oscillations were found using a freshly prepared Ce(IV), but only when the cerium-containing solution was aged, allowing partial conversion of Ce(IV) to Ce(III) by reaction with acetone. (C) 2012 Elsevier B. V. All rights reserved.

PHYSICO-CHEMICAL, SPECTROSCOPICAL AND THERMAL CHARACTERIZATION OF BIODIESEL OBTAINED BY ENZYMATIC ROUTE AS A TOOL TO SELECT THE MOST EFFICIENT IMMOBILIZED LIPASE

Two microbial lipases from Burkholderia cepacia and Pseudomonas fluorescens were evaluated as catalysts for the enzymatic transesterification of beef tallow with ethanol and the most efficient lipase source was selected by taking into account the properties of the product to be used as fuel. Both lipases were immobilized on an epoxy silica-polyvinyl alcohol composite by covalent immobilization and used to perform the reactions under the following operational conditions: beef tallow-to-ethanol molar ratio of 1:9, 45 degrees C and 400 units of enzymatic activity per gram of fat. Products, characterized using Fourier Transform Infrared spectroscopy (FTIR), viscosimetry, thermogravimetry and H-1 NMR spectroscopy, suggested that the biodiesel sample obtained in the reaction catalyzed by Burkholderia cepacia lipase has the best set of properties for fuel usage.

Steam explosion pretreatment reproduction and alkaline delignification reactions performed on a pilot scale with sugarcane bagasse for bioethanol production

This work was focused on the steam explosion pretreatment reproduction and alkaline delignification reactions on a pilot scale for the ethanol production, through different varieties of natural sugarcane bagasse, pretreated bagasse and delignified pretreated bagasse (cellulosic pulp). The possible chemical composition differences of the various types of bagasse, as well as the chemical composition variations of the materials in the 20 processes of pretreatment and delignification on the pilot scale were verified. The analytical results of the 20 samples of most diverse varieties and origins of natural sugarcane bagasse considering planting soils, planting periods and weather; show no significant chemical differences. It is evident that only with the chemical composition it is not possible to verify the differences between the varieties of sugarcane bagasses. The research results may offer some evidences of these varieties, but it is not a reliable parameter. The pilot process of steam explosion pretreatment and the alkaline delignification process of pretreated material showed through analytical results a good capacity of reproduction, as the standard differences were below 2.7. The average allowed in the pretreatment and alkaline delignification processes were 66.1 +/- 0.8 and 51.5 +/- 2.6 respectively, ensuring an excellent reproduction capacity of the processes obtained through chemical characterizations. (C) 2011 Elsevier B.V. All rights reserved.

Exergy efficiency analysis of chemical and biochemical stages involved in liquid biofuels production processes

Liquid biofuels can be produced from a variety of feedstocks and processes. Ethanol and biodiesel production processes based on conventional raw materials are already commercial, but subject to further improvement and optimization. Biofuels production processes using lignocellulosic feedstocks are still in the demonstration phase and require further R&D to increase efficiency. A primary tool to analyze the efficiency of biofuels production processes from an integrated point of view is offered by exergy analysis. To gain further insight into the performance of biofuels production processes, a simulation tool, which allows analyzing the effect of process variables on the exergy efficiency of stages in which chemical or biochemical reactions take place, were implemented. Feedstocks selected for analysis were parts or products of tropical plants such as the fruit and flower stalk of banana tree, palm oil, and glucose syrups. Results of process simulation, taking into account actual process conditions, showed that the exergy efficiencies of the acid hydrolysis of banana fruit and banana pulp were in the same order (between 50% and 60%), lower than the figure for palm oil transesterification (90%), and higher that the exergy efficiency of the enzymatic hydrolysis of flower stalk (20.3%). (C) 2011 Elsevier Ltd. All rights reserved.

Solvent Effect in Reactions Using Stryker's Reagent

The solvent has a significant influence in the rate of reactions promoted by Stryker's reagent The reactions performed in THF were, in most cases, faster than in toluene.

Thermodynamics of Axial Substitution and Kinetics of Reactions with Amino Acids for the Paddlewheel Complex Tetrakis(acetato)chloridodiruthenium(II,III)

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru-2(CH3COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters Delta H degrees, Delta S degrees, and Delta V degrees were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru-2 substituted species. The results revealed that the [Ru-2(CH3COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.