Numerical modelling of residual flow and salinity in the Río de la Plata

The Río de la Plata discharges into the Atlantic Ocean. The particular characteristics of the study area, the variable width and shallowness of the river, the high fluvial discharges and the dynamic processes involving interactions between river discharges, tidal currents and wind, generate complex velocity and salinity fields. We applied the hydrodynamic model RMA-10 to examine the effects of various forcing (tides, flow discharge and winds) on residual currents and salinity fields in the Río de la Plata, focusing on the outer zone of the river. The RMA-10 code, developed by Ian King, is a multiparameter finite element model representing estuarine flow in three dimensions. In this study the model has been applied in a depth-averaged-baroclinic mode and a series of observed data is used for model calibration and verification. The model result shows that it is able to simulate velocity and the salinity fields with a reasonable accuracy. The analysis of residual currents in the river, when forced by freshwater discharge and astronomical tide, shows that the flow discharge takes place mainly over the shallower areas of the river and that the saline water is advected up-river through the deeper channels. The numerical simulations show that the winds from the South-West and North-East quadrants have a great influence over the salinity and velocity fields.     

New formulation of iterative substructuring methods without Lagrange multipliers: Neumann–Neumann and FETI

This article is devoted to introduce a new approach to iterative substructuring methods that, without recourse to Lagrange multipliers, yields positive definite preconditioned formulations of the Neumann–Neumann and FETI types. To my knowledge, this is the first time that such formulations have been made without resource to Lagrange multipliers. A numerical advantage that is concomitant to such multipliers‐free formulations is the reduction of the degrees of freedom associated with the Lagrange multipliers. Other attractive features are their generality, directness, and simplicity. The general framework of the new approach is rather simple and stems directly from the discretization procedures that are applied; in it, the differential operators act on discontinuous piecewise‐defined functions. Then, the Lagrange multipliers are not required because in such an environment the functions‐discontinuities are not an anomaly that need to be corrected. The resulting algorithms and equations‐systems are also derived with considerable detail. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2008     

Reactivity of the anti-Criegee intermediate of β-pinene with prevalent atmospheric species

Structural Chemistry - The reaction of the anti-Criegee intermediate (anti-CI) of β-pinene with prevalent atmospheric species has been investigated using quantum-chemical calculations. The...     

Enhanced metabolite identification with MS(E) and a semi-automated software for structural elucidation

The identification of metabolites is almost exclusively done with liquid chromatography/tandem mass spectrometry (LC/MSMS) and despite the enormous progress in the development of these techniques and software for handling of data this is a time-consuming task. In this study the use of quadrupole time-of-flight (QTOF)-generated MS(E) and MS/MS data were compared with respect to rationalization of metabolites. In addition Mass-MetaSite, a semi-automated software for metabolite identification, was evaluated. The program combines the information from MS raw data, in the form of collision-induced dissociation spectra, with a prediction of the site of metabolism in order to assign the structure of a metabolite. The aim of the software is to mimic the rationalization of fragment ions performed by a biotransformation scientist in the process of structural elucidation. For this evaluation, metabolite identification in human liver microsomes was accomplished for 19 commercially available compounds and 15 in-house compounds. The results were very encouraging and for 96% of the metabolites the same structures were assigned using MS(E) compared with MSMS acquired data. The possibility of using MS(E) could considerably reduce the analysis time. Moreover, Mass-MetaSite performed well and the correct assigned structure, compared to manual inspection of the data, was picked in the first rank in ～80% of the cases. In conclusion MS(E) could be successfully used for metabolite identification in order to reduce time of analysis and Mass-MetaSite could alleviate the work of a biotransformation scientist and decrease the workload by assigning the structure for a majority of the metabolites.     

Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol

A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH···O hydrogen bond, whereas 2H-I has an OH···N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.     

A preliminary information about continuous fermentation using cell recycling for improving microbial xylitol production rates

Xylitolis a sugar-alcohol with important technological properties, such as anticariogenicity, low caloric value, and negative dissolution heat. It can be used successfully in food for mulations and pharmaceutical industries. Its production is therefore in great demand. Biotechnological xylitol production has several economic advantages in comparison with the conventional process based on the chemical reduction of xylose. The efficiency and the productivity of this fermentation chiefly depends on the microorganism and the process conditions employed. In this article a simple continuous culture with cell recycling was evaluated to enhance the capability of Candida guilliermondii FTI 20037 to produce xylitol. The fermentation was initiated batchwise by directly inoculating the grown seed culturein a 2-L bench-scale fermentor. Continuous feeding was begun at a dilution rate (D) of 0.060/h after the xylose concentration had completely consumed and the cell concentration was a bout 4.0 g/L. At a dilution rate of 0.060/h the xylitol concentration was about 15g/L and in creased by about 35%, whereas the dilution rate decreased by about 58%. Furthermore, the volumetric productivity, Q_p, markedly depended on the dilution rate, diminishing by about 37% as D was changed from 0.060 to 0.025/h. These preliminary results show us that the continous fermentation with cell recycling is a good way to study the xylitol production by xylose-fermenting yeasts.     

Efficient numerical analysis of optical imaging data: A comparative study

The computational efficiency of 14 optical detectors over six types of transformations, namely: blur, illumination, rotation, viewpoint, zoom, and zoom-rotation changes, was analyzed. Images with the same resolution (750 × 500 pixels) were studied, in terms of correspondences, repeatability and computing time, and the correspondence was measured by using homographies i.e. projective transformations, to obtain the best efficiency for imaging applications. Results show that the multi-scale Harris Hessian detector is the most efficient for blur, illumination, and zoom-rotation changes. Meanwhile, multi-scale Hessian and Hessian Laplace are the best methods for rotation, viewpoint, and zoom changes.