Optimal design of a hoist structure frame

In an attempt to find the most cost effective design of a multipurpose hoisting device that can be easily mounted on and removed from a regular farm vehicle, cost optimisation including both material and manufacturing expenditure, is performed on the main frame supporting the device. The optimisation is constrained by local and global buckling and fatigue conditions. Implementation of Snyman’s gradient-based LFOPC optimisation algorithm to the continuous optimisation problem, results in the economic determination of an unambiguous continuous solution, which is then utilised as the starting point for a neighbourhood search within the discrete set of profiles available, to attain the discrete optimum.

This optimum is further investigated for a different steel grade and for the manufacturing and material cost pertaining to different countries. The effect of variations in the formulation of the objective function for optimisation is also investigated. The results indicate that considerable cost benefits can be obtained by optimisation, that costing in different countries do not necessarily result in the same most cost effective design, and that accurate formulation of the objective function, i.e. realistic mathematical modelling, is of utmost importance in obtaining the intended design optimum.     

Selective ion-exchanger behaviour of neutral carrier ion-selective electrode membranes

Radiotracer experiments confirm that neutral carrier ion-selective electrodes made from plasticized PVC are low-capacity selective ion-exchangers. The ion-exchange selectivity is closely correlated to potentiometric selectivity.     

Transfinite Diameter, Chebyshev Constant and Energy on Locally Compact Spaces

We study the relationship between transfinite diameter, Chebyshev constant and Wiener energy in the abstract linear potential analytic setting pioneered by Choquet, Fuglede and Ohtsuka. It turns out that, whenever the potential theoretic kernel satisfies the maximum principle, then all these quantities are equal for all compact sets. For continuous kernels even the converse statement is true: if the Chebyshev constant of any compact set coincides with its transfinite diameter, the kernel must satisfy the maximum principle. An abundance of examples is provided to show the sharpness of the results. Dedicated to the memory of Professor Gustave Choquet (1 March 1915–14 November 2006).     

Mechanism for the reactions of sulfides and sulfoxides with hypochlorites: racemization and oxygen exchange of oxysulfonium salts and sulfoxides

Density functional theory computations have been performed on the oxidations of sulfides and sulfoxides with hypochlorite ion (OCl^?), hypochlorous acid, and alkyl hypochlorites to study the mechanism of the reactions. The OCl^? anion transforms sulfides to sulfoxides and sulfoxides to sulfones in oxygen transfers. The oxygen atom of QOCl hypochlorites (Q = H, Me, t‐Bu) attacks at the sulfur atom of the substrates, and oxysulfonium cation intermediates are formed; the departure of the leaving Cl^? is catalyzed by soft Lewis acids. The structures of the early transition states are determined by highest occupied molecular orbital–lowest unoccupied molecular orbital interactions. The sulfur compounds are the electron acceptors in the reaction with OCl^?, but they are the electron donors in the reactions with QOCl. The attack of Cl^? at the oxygen atom of oxysulfonium cation intermediates leads to the sulfide and QOCl precursors and can result in racemization, oxygen exchange, and reduction of oxysulfonium salts in reversible reactions. The attack of Cl^? at the sulfur atom of oxysulfonium salts produces λ⁴‐sulfane intermediates. Oxysulfonium cations can be transformed into sulfoxide products with the attack of Cl^? or water at the α‐carbon atom of the O‐alkyl group. The attack of water at the sulfur atom of oxysulfonium cation leads to hydrolysis or oxygen exchange reactions. Racemization and oxygen exchange of sulfoxides proceeds in similar reactions, through the formation of hydroxysulfonium cation intermediates in acidic media in the presence of Cl^?. Chlorosulfonium cations are of very high energy; their intermediacy can be ruled out in the reactions of sulfides with hypochlorites. Copyright © 2012 John Wiley & Sons, Ltd.     

Prospects in computational molecular medicine: a millennial mega-project on peptide folding

During the second half of the 20th century, Molecular Computations have reached to a level that can revolutionize chemistry. The next target will be structural biology, which will be followed soon by Molecular Medicine. The present paper outlines where we are at, in this field, at the end of the 20th century, and in what direction the development may take in the new millennium. In view of the gigantic nature of the problem, it is suggested that a suitably designed cooperative Millennial Mega-project might accelerate our schedule.     

Validated HPLC Method for Simultaneous Quantitation of Bergenin,Arbutin, and Gallic Acid in Leaves of Different Bergenia Species

Bergenia species (Saxifragaceae) are important sources of herbal medicines in Asia, mainly in Russia. Various plant parts are valued for their antibacterial, anti-inflammatory, antioxidant sand adaptogenic effect, and used for the dissolution of kidney and bladder stones. In this study a rapid reversed phase liquid chromatography (RP-HPLC) method has been developed for rapid screening and identifying of the main active components in leaf samples of Bergenia accessions. The main goal of this study was to develop an efficient method for the simultaneous identification and detection of arbutin, bergenin and gallic acid from Bergenia leaf samples, which were extracted with a methanolic solvent mixture [methanol:water = 1:1 (v/v)]. Chromatographic separations were performed on a reversed phase Luna C18(2)-HST HPLC column. This chromatographic system provided increased speed and efficiency for separations, without the need for ultra-high pressures. Reversed phase HPLC coupled with diode array detector method was used for the analysis. The method was validated using ICH guidelines. The level of gallic acid was significantly higher in Bergenia crassifolia samples compared to Bergenia cordifolia. However, the samples of the two Bergenia species did not differ substantially regarding the concentrations of arbutin and bergenin. The novel method proved to be fast and allowed sufficient separation and quantification of arbutin, bergenin and gallic acid, the most important bioactive compounds of Bergenia leaves; thus facilitating rapid screening and quality assessment of Bergenia samples of various botanical and geographical origins.

     

Effect of substituents on activation parameters in aliphatic S(N)2 reactions. A DFT study

The activation parameters and optimized structures of the reactants and transition states in the S(N)2 reactions of substituted pyridines and N,N-dimethylanilines with methyl iodide were computed at the DFT level in different solvents. The measured and calculated deltaG/deltaH/deltaS versus sigma plots proved to be linear, and their slopes, the deltadeltaG, deltadeltaH, and deltadeltaS reaction constants, were determined. The least solvent-dependent deltadeltaG reaction constants can be computed with acceptable accuracy. The calculated deltadeltaS data decrease only very slightly with the jointly increasing electron-withdrawing effect of the substituents and tightness of the transition states. The measured deltadeltaS values are influenced mainly by the change of solvation in the reactions, and deltadeltaH is also influenced by the reorganization of the solvent. Consequently, the experimental and calculated deltadeltaS and deltadeltaH reaction constants may deviate considerably from each other. In dipolar aprotic solvents the measured deltadeltaS was less than zero, and in protic solvents it was greater than zero. The ordering of the solvent molecules around the transition state with increasing charge is increased in the former but decreased in the latter media, as compared to the bulk of the solvents. The calculated deltaG(o), deltaH(o), and deltaS(o) parameters of the unsubstituted compounds agree relatively well with the experimental data for reactions of neutral molecules in dipolar aprotic solvents (e.g., XC6H4N(CH3)2 + CH3I). On the other hand, the measured and calculated activation parameters may show considerable deviations for reactions of ions (e.g., XC5H4NCH3+ + I-) and for any reaction in protic solvents.     

Random Walk of Second Class Particles in Product Shock Measures

We consider shock measures in a class of conserving stochastic particle systems on ℤ. These shock measures have a product structure with a step-like density profile and include a second class particle at the shock position. We show for the asymmetric simple exclusion process, for the exponential bricklayers’ process, and for a generalized zero range process, that under certain conditions these shocks, and therefore the second class particles, perform a simple random walk. Some previous results, including random walks of product shock measures and stationary shock measures seen from a second class particle, are direct consequences of our more general theorem. Multiple shocks can also be handled easily in this framework. Similar shock structure is also found in a nonconserving model, the branching coalescing random walk, where the role of the second class particle is played by the rightmost (or leftmost) particle.     

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

Journal of Thermal Analysis and Calorimetry - A simple synthetic method was developed to prepare 4[Agpy2ClO4]·[Agpy4]ClO4 in a low-temperature decomposition process of [Agpy4]ClO4. A detailed...