A study of the cu clusters using gray-coded genetic algorithms and differential evolution

Energy minimization studies were carried out for a number of Cu clusters using binary and Gray-coded genetic algorithms along with real coded differential evolution, and their optimized ground state geometries are presented. The potential energy function is constructed using a two-body interaction methodology, involving both attractive and repulsive pair-potential terms. The results obtained through the evolutionary algorithms are compared against those obtained earlier using a Monte Carlo technique.     

Preparation of ketoprofen‐loaded high‐molecular‐weight poly(vinyl alcohol) gels

High‐molecular‐weight atactic poly(vinyl alcohol) (a‐PVA) gels loaded with (R,S)‐2‐(3‐benzoylphenyl)propionic acid (ketoprofen) were prepared from 5, 6, 7, and 8 g/dL solutions of a‐PVA with a number‐average degree of polymerization of 4000 in an ethylene glycol/water mixture with an aging method to identify the effect of the initial polymer concentration on the swelling behavior, morphology, and thermal properties of a‐PVA gels. Then, the release behavior of ketoprofen from a‐PVA gels was investigated. As the polymer concentration decreased, the ability for network formation decreased, and the degree of swelling of the a‐PVA gels increased. In addition, the enthalpy increased with an increase in the a‐PVA concentration, but the melting temperatures of the gels prepared at different initial polymer concentrations were the same; this indicated that tighter gel networks would be formed by a higher polymer chain density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Determination of the adhesion force between particles and a flat surface, using the centrifuge technique

By using a centrifuge technique, the influence of powdery material particle size on the adhesion force particle-surface was determined. In order to achieve this, the adhesion of phosphatic rock (ρ_p = 3.090 kg m^− 3) and of manioc starch particles (ρ_p = 1.480 kg m^− 3) on a steel surface were studied. A microcentrifuge that reached a maximum speed rotation of 14000 rpm and which contained specially designed centrifuge tubes was used. There tubes contained the flat surface where the test particles were deposited. The powder particles were dispersed on these disks and the particles detachment were performed using diverse centrifugal speeds. The graphics of particle percentages still adhering on the surface of the disks as a function of the applied detachment force showed that the profile of adhesion force followed a log-normal distribution. The adhesion force increased with particle size. The manioc starch particles presented adhesion forces greater than those for the phosphatic rock particles for all particle sizes studied. The results obtained were compared with the theory proposed by Derjaguin, Muller and Toporov whose theoretical adhesion presented values close to the experimental data for the phosphatic rock particles adhesion on the stainless steel surface. On the contrary, the theoretical values were lower than the experimental ones for the manioc starch particles maybe due to the small roughness of these particles, their physical properties (softer and deformable material) and/or specific chemical interactions since the organic composition of the manioc starch particles that can dominate the adhesion force. Finally, the separation distance among the surfaces in contact (Z₀) was estimated in approximately 1.0 × 10^− 9 m for the phosphatic rock and 5.0 × 10^− 10 m for the manioc starch. These results were weakly dependent on the particle size range.     

Predicting and tuning physicochemical properties in lead optimization: amine basicities

This review describes simple and useful concepts for predicting and tuning the pK(a) values of basic amine centers, a crucial step in the optimization of physical and ADME properties of many lead structures in drug-discovery research. The article starts with a case study of tricyclic thrombin inhibitors featuring a tertiary amine center with pK(a) values that can be tuned over a wide range, from the usual value of around 10 to below 2 by (remote) neighboring functionalities commonly encountered in medicinal chemistry. Next, the changes in pK(a) of acyclic and cyclic amines upon substitution by fluorine, oxygen, nitrogen, and sulfur functionalities, as well as carbonyl and carboxyl derivatives are systematically analyzed, leading to the derivation of simple rules for pK(a) prediction. Electronic and stereoelectronic effects in cyclic amines are discussed, and the emerging computational methods for pK(a) predictions are briefly surveyed. The rules for tuning amine basicities should not only be of interest in drug-discovery research, but also to the development of new crop-protection agents, new amine ligands for organometallic complexes, and in particular, to the growing field of amine-based organocatalysis.     

A novel method for color determination of edible oils in L*a*b* format

A simple method that uses visible spectrophotometer data and an artificial neural network (ANN) was developed to determine edible oil color based on the L*a*b* format. The 100 oil samples consisted of nine pure oils, a sesame oil blend and three heated oils. Binary, ternary and quaternary mixtures of these 13 oils in different ratios were prepared, and absorbance values of the samples were measured in the visible region (380–700 nm). The absorbance values at wavelengths of 416, 456, 483, 537, 611 and 672 nm were used to train, validate and test the network. Strong correlations between the instrumental L*a*b*ΔE and the estimated L*a*b*ΔE were found for the test samples, with correlation coefficients (R²) of 0.989, 0.984, 0.996 and 0.992 for L*, a*, b*, and ΔE, respectively. The effects of number and combination of the wavelengths used for training of the ANN on the estimation capability of the network for the test samples were also investigated. Although a good agreement, average R² of 0.991– 0 993 for L*a*b*, was obtained for combinations composed of three to six wavelengths with 483 and 537 nm in common, the best R² value was obtained when all six wavelengths were used to train the ANN. The developed method is objective, cost effective and simple, and allows the color measurement with a basic visible spectrophotometer and disposable cuvettes.     

Determination of tocopherols and phytosterols in sunflower seeds by NIR spectrometry

The objective of this work was to develop a near‐infrared reflectance spectrometry (NIRS) calibration estimating the tocopherol and phytosterol contents in sunflower seeds. Approximately 1000 samples of grinded sunflower kernels were scanned by NIRS at 2‐nm intervals from 400 to 2500 nm. For each sample, standard measurements of tocopherol and phytosterol contents were performed. The total tocopherol content was obtained by high‐performance liquid chromatography coupled with a fluorescence detector, while the total phytosterol content was assessed by gas chromatography. For tocopherol, the calibration data set ranged from 175 to 1005 mg/kg oil (mean value around 510 ± 140 mg/kg oil), whereas for the phytosterol content, the calibration data set ranged from 180 to 470 mg/100 g oil (mean value of 320 ± 50 mg/100 g oil). The NIRS calibration showed a relatively good correlation (R² = 0.64) between predicted by NIRS and real values for the total tocopherol content but a poor correlation for the total phytosterol content (R² = 0.27). These results indicate that NIRS could be useful to classify samples with high and low tocopherol content. In contrast, the estimation of phytosterol contents by NIRS needs further investigation. Moreover, in this study, calibration was obtained by a modified partial least‐squares method; the use of other mathematical treatments can be suitable, particularly for total phytosterol content estimation.     

Experimental Tests and Modelling of an Electrodeionization Cell for the Treatment of Dilute Copper Solutions

The paper presents the results of experimental and theoretical investigations of an electrodeionization process for the removal of metal cations from dilute solutions. The ability of this technique to treat 100 ppm copper solutions using cationic membranes and ion‐exchange resins between the membranes was studied. Fair abatement yields were obtained in the 100 mm high resin bed in long‐term runs, and solutions of an appreciable copper ion concentration could be produced in the cathode chamber. The process capacity was limited by significant deposition of copper at the cathode, non‐even distribution of current density, and side‐diffusion to the anode chamber. Additional tests were then carried out using a 15 mm resin bed. The more even current distributions allowed the effect of the resin stiffness and the current density on the removal yield to be thoroughly observed. Steady‐state operation of the resin bed was modelled using generalized expressions of the various transport rates. Results of the model clearly showed the significance of solid‐liquid interactions on the transport processes.     

Activities of MFI-Supported Rhenium Catalysts for the Aromatization of Methane: Effect of Cationic Form of the Inorganic Carrier

MFI type inorganic carrier was used in two different cationic forms, hydrogen and calcium respectively. MFI-supported molybdenum and rhenium catalysts were prepared. The activities of the catalysts were compared for the aromatization reaction of methane. Higher activity values were attained with the catalysts supported on HZSM-5. Aromatics were also observed with the catalysts supported on CaZSM-5, despite their deficiency in acid sites. Highly dispersed rhenium is expected to be formed with the use of the inorganic carrier in calcium form. On the other hand, lower reaction rates were observed with rhenium supported on CaZSM-5, in spite of the improved dispersion of the active rhenium species on this catalyst. This was interpreted in terms of the critical role of the acid sites in the conversion of methane to aromatics, compared to the improved dispersion of the active metal.     

Effects of some additives on the corrosion behaviour and preferred orientations of zinc obtained by continuous current deposition

The effect of thiourea, urea and guanidin on zinc deposits obtained from chloride baths under continuous current conditions are described and discussed. The corrosion behaviour of the deposits was investigated in an aerated 3.5% NaCl solution; anodic polarization curves, polarization resistance (R _p) measurements and weight-loss studies were performed. The corrosion resistance of zinc deposits improved in the presence of urea. The deposit morphology was analyzed using Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) was used to determine the preferred crystallographic orientations of the deposits. The preferred crystallographic orientations of zinc deposits (112) do not change in the presence of urea and guanidin except for an increase in the peak intensity of the (112) plane. In the presence of thiourea, zinc deposits crystallise in two textures; (100) and (110). The influence of each additive and the difference between additives on the zinc deposits are also discussed.     

Potential for use of crushed waste calcined-clay brick as a supplementary cementitious material in Brazil

The Brazilian ceramic industry generates large amounts of calcined-clay waste. This paper examines the factors that influence its potential for use as a partial replacement of Portland cement. Superplasticized mortars of equal workability containing ground crushed waste calcined-clay brick (GCWCCB) in the proportions of 10, 20, 30 and 40% as a cement replacement were analyzed through mechanical tests, pore structure characterization and durability tests. The results indicated the optimal percentages of substitution lies between 10% to 20%. The potential reduction of CO₂ emissions could be as high as 10% of current Brazilian cement industry emissions if this approach were to be fully implemented, and it could be eligible for “Clean Development Mechanism” credits under Kyoto protocol.