Application of high-resolution electrospray mass spectrometry for the elucidation of the disproportionation reaction of iodobenzene diacetate

Disproportionation reactions take place in solution of (diacetoxyiodo)benzene (DIB) in acetonitrile in the presence of water, giving iodine(V) and iodine(l) species. This redox reaction is accelerated by the presence of water and by increasing the temperature. Several species of the solution of DIB were identified by high-resolution ESI-MS/MS, which allowed the elucidation of the mechanisms of disproportionation for DIB in gas phase and in solution. Key species in the process are the dimers [PhI(CH)OlPh](+) at m/z 440.8864, [PhI(OAc)OlPh](+) at m/z 482.8947, and [PhI(O)(OAc)OlPh](+) at m/z 498.8887. (C) 2008 Elsevier B.V. All rights reserved.

Effect of the Maillard reaction on properties of casein and casein films

The use of biodegradable natural polymers has increased due to the over-solid packaging waste. In this study, a chemical modification of the casein molecule was performed by Maillard reaction, and the modified polymer was evaluated by polyacrylamide gel electrophoresis (PAGE), thermogravimetry/derivative thermogravimetry (TG/DTG), FT-IR, and (1)H-NMR spectroscopy. Subsequently, films based on the modified casein were obtained and characterized by mechanical analysis, water vapor transmission, and erosion behavior. The PAGE results suggested an increase of molecular mass of the modified polymer, and FT-IR spectroscopy data indicated inclusion of C-OH groups into this molecule. The TG/DTG curves of modified casein presented a different thermal decomposition profile compared to the individual compounds. Mechanical tests showed that the chemical modification of the casein molecules provided higher elongation rates (45.5%) to the films, suggesting higher plasticity, than the original molecules (13.4%). The modified casein films presented higher permeability (0.505 +/- A 0.006 mu g/h mm(3)) than the original polymer (0.387 +/- A 0.006 mu g/h mm(3)) films at 90% relative humidity (RH). In pH 1.2, modified casein films presented higher erosion rates (32.690 +/- A 0.692%) than casein films (19.910 +/- A 2.083%) after 8 h, suggesting an increased sensibility for erosion of the modified casein films in acid environment. In water (pH 7.0), the films erosion profiles were similar. Those findings indicate that the modification of molecule by Maillard reaction provided films more plastic, hydrophilic, and sensitive to erosion in acid environment, suggesting that a new polymer with changed properties was founded.

Functionalization of (2S)-Isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones by a Suzuki-Miyaura Cross-Coupling Reaction Using Aryltrifluoroborate Salts: Convenient Enantioselective Preparation of alpha-Substituted beta-Amino Acids

A simple protocol for the Pd(OAc)(2)-catalyzed cross-coupling reaction of 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones with potassium aryltrifluoroborates was developed. The reaction is performed at 110 degrees C with a ligand-free catalyst. In all cases, complete conversion of the 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones and aryltrifluoroborates into the C-C coupling products was observed within 30-360 min. It is noteworthy that a large variety of groups present in the potassium aryltrifluoroborates (-CF(3), -OMe, -SEt, -CN, -CHO, -Cl, -Cbz, -NCbz, -OH, -CO(2)H) could be tolerated. Hydrogenation of the endocyclic double bonds in the Suzuki-Miyaura products followed by acid hydrolysis afforded highly enantioenriched alpha-aryl-substituted beta-amino acids.

Synthesis of symmetrical 1,3-diynes via homocoupling reaction of n-butyl alkynyltellurides

An ultrasound-assisted synthesis of symmetrical 1,3-diyne compounds with electron-withdrawing or donating substituents is described and illustrated by the palladium-catalyzed homocoupling reaction of n-butyl alkynyltellurides. This procedure offers easy access to 1,3-diynes in very short reaction times, and the products are achieved in good to excellent yields. (C) 2009 Elsevier Ltd. All rights reserved.

Molecular Sieve Silica (MSS) Membranes for Gas Separation and Reaction Processes

Weakly branched silica films formed by the two-step sol-gel process allow for the formation of high selectivity membranes for gas separation. 29Si NMR and gas permeation showed that reduced crosslinking leads to He/CH4 selectivity improvement from 300 to 1000. Applied in membrane reactor for cyclohexane conversion to benzene, conversions were achieved at 14 fold higher than a conventional reactor at 250°C. Hydrothermal stability studies showed that carbon templating of silica is required for hydrothermally stable membranes. From our work it was shown that with correct application of chemistry, practical membrane systems can be built to suit gas separation (e. g. hydrogen fuel) and reactor systems.

A modified discrete random pore model allowing for different initial surface reactivity

We investigate here a modification of the discrete random pore model [Bhatia SK, Vartak BJ, Carbon 1996;34:1383], by including an additional rate constant which takes into account the different reactivity of the initial pore surface having attached functional groups and hydrogens, relative to the subsequently exposed surface. It is observed that the relative initial reactivity has a significant effect on the conversion and structural evolution, underscoring the importance of initial surface chemistry. The model is tested against experimental data on chemically controlled char oxidation and steam gasification at various temperatures. It is seen that the variations of the reaction rate and surface area with conversion are better represented by the present approach than earlier random pore models. The results clearly indicate the improvement of model predictions in the low conversion region, where the effect of the initially attached functional groups and hydrogens is more significant, particularly for char oxidation. It is also seen that, for the data examined, the initial surface chemistry is less important for steam gasification as compared to the oxidation reaction. Further development of the approach must also incorporate the dynamics of surface complexation, which is not considered here.

Geochronology of weathering and landscape evolution, Dugald River valley, NW Queensland, Australia

40Ar/39Ar laser incremental heating analyses of individual grains of supergene jarosite, alunite, and cryptomelane from weathering profiles in the Dugald River area, Queensland, Australia, show a strong positive correlation between a sample’s age and its elevation. We analyzed 125 grains extracted from 35 hand specimens collected from weathering profiles at 11 sites located at 3 distinct elevations. The highest elevation profile hosts the oldest supergene minerals, whereas progressively younger samples occur at lower positions in the landscape. The highest elevation sampling sites (three sites), located on top of an elongated mesa (255 to 275 m elevation), yield ages in the 16 to 12 Ma range. Samples from an intermediate elevation site (225 to 230 m elevation) yield ages in the 6 to 4 Ma range. Samples collected at the lowest elevation sites (200 to 220 m elevation) yield ages in the 2.2 to 0.8 Ma interval. Grains of supergene alunite, jarosite, and cryptomelane analyzed from individual single hand specimens yield reproducible results, confirming the suitability of these minerals to 40Ar/39Ar geochronology. Multiple samples collected from the same site also yield reproducible results, indicating that the ages measured are true precipitation ages for the samples analyzed. Different sites, up to 3 km apart, sampled from weathering profiles at the same elevation again yield reproducible results. The consistency of results confirms that 40Ar/39Ar geochronology of supergene jarosite, alunite, and cryptomelane yields ages of formation of weathering profiles, providing a reliable numerical basis for differentiating and correlating these profiles. The age versus elevation relationship obtained suggest that the stepped landscapes in the Dugald River area record a progressive downward migration of a relatively flat weathering front. The steps in the landscape result from differential erosion of previously weathered bedrock displaying different susceptibility to weathering and contrasting resistance to erosion. Combined, the age versus elevation relationships measured yield a weathering rate of 3.8 m. Myr−1 (for the past 15 Ma) if a descending subhorizontal weathering front is assumed. The results also permit the calculation of the erosion rate of the more easily weathered and eroded lithologies, assuming an initially flat landscape as proposed in models of episodic landscape development. The average erosion rate for the past 15 Ma is 3.3 m. Myr−1, consistent with erosion rates obtained by cosmogenic isotope studies in the region.

Thermal effects in the evolution of initially layered mantle material

A simplified model for anisotropic mantle convection based on a novel class of rheologies, originally developed for folding instabilities in multilayered rock (MUHLHAUS et al., 2002), is extended ¨ through the introduction of a thermal anisotropy dependent on the local layering. To examine the effect of the thermal anisotropy on the evolution of mantle material, a parallel implementation of this model was undertaken using the Escript modelling toolkit and the Finley finite-element computational kernel (DAVIES et al., 2004). For the cases studied, there appears too little if any effect. For comparative purposes, the effects of anisotropic shear viscosity and the introduced thermal anisotropy are also presented. These results contribute to the characterization of viscous anisotropic mantle convection subject to variation in thermal conductivities and shear viscosities.

Maternal transmission efficiency of Wolbachia superinfections in Aedes albopictus populations in Thailand

We examined the transmission efficiency of 2 strains of Wolbachia bacteria that cause cytoplasmic incompatibility in field populations of Aedes albopictus by polymerase chain reaction assay. We found mainland and island populations throughout Thailand to be superinfected with group A and B bacteria. Of 320 Wolbachia-positive adult mosquitoes, 97.5% were infected with both groups. Single infected individuals of each Wolbachia group were encountered in nearly equal numbers. We screened 550 offspring from 80 field-collected mothers and found the transmission efficiency of group A Wolbachia to be 96.7% and that of group B Wolbachia to be 99.6%. Mothers that did not transmit both Wolbachia infections to all of their offspring were significantly larger in size than those with perfect transmission fidelity. We discuss our findings in relation to the prospects of the use of Wolbachia as a gene-driving mechanism.

Evolution of Wolbachia pipientis transmission dynamics in insects

Wolbachia pipientis is an intracellular bacterial parasite of arthropods that enhances its transmission by manipulating host reproduction, most commonly by inducing cytoplasmic incompatibility. The discovery of isolates with modified cytoplasmic incompatibility phenotypes and others with novel virulence properties is an indication of the potential breadth of evolutionary strategies employed by Wolbachia.

A finite integral transform technique for solving the diffusion-reaction equation with Michaelis-Menten kinetics

An approximate analytical technique employing a finite integral transform is developed to solve the reaction diffusion problem with Michaelis-Menten kinetics in a solid of general shape. A simple infinite series solution for the substrate concentration is obtained as a function of the Thiele modulus, modified Sherwood number, and Michaelis constant. An iteration scheme is developed to bring the approximate solution closer to the exact solution. Comparison with the known exact solutions for slab geometry (quadrature) and numerically exact solutions for spherical geometry (orthogonal collocation) shows excellent agreement for all values of the Thiele modulus and Michaelis constant.

A master equation model for bimolecular reaction via multi-well isomerization intermediates

A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.