Modelling the chemical weathering fluxes at the watershed scale in the Tropics (Mule Hole, South India): Relative contribution of the smectite/kaolinite assemblage versus primary minerals

We investigate the chemical weathering processes and fluxes in a small experimental watershed (SEW) through a modelling approach. The study site is the Mule Hole SEW developed on a gneissic basement located in the climatic gradient of the Western Ghats, South India. The model couples a lumped hydrological model simulating the water budget at the watershed scale to the WITCH model estimating the dissolution/precipitation rates of minerals using laboratory kinetic laws. Forcing functions and parameters of the simulation are defined by the field data. The coupled model is calibrated with stream and groundwater compositions through the testing of a large range of smectite solubility and abundance in the soil horizons. We found that, despite the low abundance of smectite in the dominant soil type of the watershed (4 vol.%), their net dissolution provides 75% of the export of dissolved silica, while primary silicate mineral dissolution releases only 15% of this flux. Overall, smectites (modelled as montmorillonites) are not stable under the present day climatic conditions. Furthermore, the dissolution of trace carbonates in the saprolitic horizon provides 50% of the calcium export at the watershed scale. Modelling results show the contrasted behavior of the two main soil types of the watershed: red soils (88% of the surface) are provider of calcium, while black soils (smectite-rich and characterized by a lower drainage) consumes calcium through overall carbonate precipitation. Our model results stress the key role played by minor/accessory minerals and by the thermodynamic properties of smectite minerals, and by the drainage of the weathering profiles on the weathering budget of a tropical watershed. (C) 2010 Elsevier B.V. All rights reserved.

Compensator for constant relative stability in process control systems

Process control systems are designed for a closed-loop peak magnitude of 2dB, which corresponds to a damping coefficient () of 0.5 approximately. With this specified constraint, the designer should choose and/or design the loop components to maintain a constant relative stability. However, the manipulative variable in almost all chemical processes will be the flow rate of a process stream. Since the gains and the time constants of the process will be functions of the manipulative variable, a constant relative stability cannot be maintained. Up to now, this problem has been overcome either by selecting proper control valve flow characteristics or by gain scheduling of controller parameters. Nevertheless, if a wrong control valve selection is made then one has to account for huge loss in controllability or eventually it may lead to an unstable control system. To overcome these problems, a compensator device that can bring back the relative stability of the control system was proposed. This compensator is similar to a dynamic nonlinear controller that has both online and offline information on several factors related to the control system. The design and analysis of the proposed compensator is discussed in this article. Finally, the performance of the compensator is validated by applying it to a two-tank blending process. It has been observed that by using a compensator in the process control system, the relative stability could be brought back to a great extent despite the effects of changes in manipulative flow rate.

Enantiospecific first total synthesis and confirmation of the relative and absolute stereostructure of isocalamusenone

The enantiospecific total synthesis of two epimers of the sesquiterpene isocalamusenone has been accomplished starting from the readily available monoterpene (R)-limonene which of the natural product established the stereostructure and the absolute configuration (C) 2010 Elsevier Ltd All rights reserved

A simple computational model for predicting .pi.-facial selectivity in reductions of sterically unbiased ketones. Relative importance of electrostatic and orbital interactions

Various factore controlling the preferred facial selectivity in the reductions of a number of sterically unbiased ketones have been evaluated using a semiempirical MO procedure. MNDO optimized geometries do not reveal any significant ground-state distortions which can be correlated with the observed face selectivities. Electrostatic effecta due to an approaching reagent were modeled by placing a test negative charge at a fixed distance from the carbonyl carbon on each of the two faces. A second series of calculations was carried out using the hydride ion as a test nucleophile. The latter calculations effectively include orbital interactions involving the u and u* orbitals of the newly formed bond in the reaction. The computed energy differences with the charge model are generally much larger compared to those with the hydride ion. However, both models lead to predictions which are qualitatively consistent with the experimentally determined facial preferences for most of the systems. Thus, electrostatic interactions between the nucleophile and the substrate seem to effectively determine the face selectivities in these molecules. However, there are a few exceptions in which orbital interactions are found to contribute significantly and occasionally reverse the preference dictated by electrostatic effecta. The remarkable succew of the hydride model calculations, in spite of retaining the unperturbed geometries of the substrates, points to the unimportance of torsional effeds and orbital distortions associated with the pyramidalized carbonyl unit in the transition state in most of the substrates considered. Additional experimental results are reported which provide useful calibration for the present computational approach.

Parabolic trough concentrators—design, construction and evaluation

A brief review on the design aspects of the structural, optical and thermal subsystems of parabolic trough concentrators is given. Existing methods of performance evaluation and techniques to improve their performance are also discussed.

Some new results regarding spikes and a heuristic for spike construction

his paper addresses the problem of minimizing the number of columns with superdiagonal nonzeroes (viz., spiked columns) in a square, nonsingular linear system of equations which is to be solved by Gaussian elimination. The exact focus is on a class of min-spike heuristics in which the rows and columns of the coefficient matrix are first permuted to block lower-triangular form. Subsequently, the number of spiked columns in each irreducible block and their heights above the diagonal are minimized heuristically. We show that ifevery column in an irreducible block has exactly two nonzeroes, i.e., is a doubleton, then there is exactly one spiked column. Further, if there is at least one non-doubleton column, there isalways an optimal permutation of rows and columns under whichnone of the doubleton columns are spiked. An analysis of a few benchmark linear programs suggests that singleton and doubleton columns can abound in practice. Hence, it appears that the results of this paper can be practically useful. In the rest of the paper, we develop a polynomial-time min-spike heuristic based on the above results and on a graph-theoretic interpretation of doubleton columns.

Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor

The details of the first total synthesis of a natural thapsane lg containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) '5 described. The Claisen rearrangement of 9 with methoxypropene in the presence of a catalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of a-diazo-&keto ester 12, obtained from 10 via 8-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:l mixture of hydrindanone 6 and keto1 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane

High sensitive Static fiber Bragg grating strain sensing using lasers locked to relative frequency reference

A novel high sensitive fiber Bragg grating (FBG) strain sensing technique using lasers locked to relative frequency reference is proposed and analyzed theoretically. Static strain on FBG independent of temperature can be measured by locking frequency of diode laser to the mid reflection frequency of matched reference FBG, which responds to temperature similar to that of the sensor FBG, but is immune to strain applied to the same. Difference between light intensities reflected from the sensor and reference FBGs (proportional to the difference between respective pass band gains at the diode laser frequency) is not only proportional to the relative strain between the sensor and reference FBGs but also independent of servo residual frequency errors. Usage of relative frequency reference avoids all complexities involved in the usage of absolute frequency reference, hence, making the system simple and economical. Theoretical limit for dynamic and static strain sensitivities considering all major noise contributions are of the order of 25 (p epsilon) / root Hz and 1.2 n epsilon / root Hz respectively.

The Design and Construction of Synthetic Protein Mimics

A strategy for the modular construction of synthetic protein mimics based on the ability non-protein amino acids to act as stereochemical directors of polypeptide chain folding, is described. The use of alpha-aminoisobutyric acid (Aib) to construct stereochemically rigid helices has been exemplified by crystallographic and spectroscopic studies of several apolar peptides, ranging in length from seven to sixteen residues. The problem of linker design in elaborating alpha,alpha motifs has been considered. Analysis of protein crystal structure data provides a guide to choosing linking sequences. Attempts at constructing linked helical motifs using linking Gly-Pro segments have been described. The use of flexible linkers, like epsilon-aminocaproic acid has been examined and the crystallographic and solution state analysis of a linked helix motif has been presented. The use of bulky sidechain modifications on a helical scaffold, as a means of generating putative binding sites has been exemplified by a crystal structure of a peptide packed in a parallel zipper arrangement.

Enantiospecific synthesis and confirmation of the relative and absolute stereostructure of 11-hydroxyguaiadienes

Enantiospecific total synthesis of two epimeric sesquiterpenes 11-hydroxyguaiadienes has been accomplished starting from the readily available monoterpene (R)-limonene, which confirmed the structure and absolute configuration of the natural products. (C) 2010 Elsevier Ltd. All rights reserved.

Construction of energy-level diagram of oriented benzene using connectivity information obtained by modified z-cosy experiment

Experiments involving selective perturbation of a transition yield information about the directly connected transitions, which in turn yield information for deriving the parameters of the spin Hamiltonian of oriented molecules. Problems involved with selective perturbation are removed by the use of a two-dimensional experiment, namely, the modified Z-COSY-experiment, The use of this experiment is demonstrated for obtaining the connectivity information and for determining the parameters of the spin Hamiltonian of oriented benzene, a strongly coupled six-spin system