Zeolites as catalysts in organic reactions. Claisen-Schmidt condensation of acetophenone with benzaldehyde

HY zeolites catalyze the crossed aldol condensation of acetophenone with benzaldehyde, in benzene at 80 °C, to give trans- and cis-chalcones. Together with these expected products, 3,3-diphenylpropiophenone is also produced. In the analogous basic condensation, using phase transfer catalysis, the Michael adduct was not detected, and besides chalcone a small percentage of the Cannizzaro reaction product was observed.     

Electrocatalytic oxidation of ethanol on Pt–Mo bimetallic electrodes in acid medium

Pt–Mo alloy electrocatalysts were prepared by an arc-melting furnace process to investigate the origin of their enhanced activity toward ethanol oxidation. Two Mo contents were chosen in zones of the binary phase diagram where they are supposed to form either a pure alloy mixture or a solid solution. Pt–Mo alloy catalysts were more active than Pt-alone. Gradual Mo dissolution at the electrode surface was observed after voltammetric and chronoamperometric measurements. The dissolved Mo contributed to the catalytic effect of the electrode as underpotentially deposited (upd) adatoms. This dissolution probably also leads to an increase in the electrode surface roughness. Low molybdenum content in the electrode material enhances the activity toward ethanol oxidation when compared to Pt-alone. Ethanol oxidation was also investigated by in situ infrared reflectance spectroscopy in order to determine the presence of adsorbed intermediates like CO species. Acetaldehyde, acetic acid and CO₂ were also found by spectroscopic experiments.     

Lightweight dynamic symmetry breaking

Symmetries in constraint problems present an opportunity for reducing search. This paper presents Lightweight Dynamic Symmetry Breaking, an automatic symmetry breaking method that is efficient enough to be used as a default, since it never yields a major slowdown while often giving major performance improvements. This is achieved by automatically exploiting certain kinds of symmetry that are common, can be compactly represented, easily and efficiently processed, automatically detected, and lead to large reductions in search. Moreover, the method is easy to implement and integrate in any constraint system. Experimental results show the method is competitive with the best symmetry breaking methods without risking poor performance.     

Computational Aspects of Uncertainty Profiles and Angel-Daemon Games

We analyze the complexity of equilibria problems for a class of strategic zero-sum games, called angel-daemon games. Those games were introduced to asses the performance of the execution of a web orchestration on a moderate faulty or under stress environment. Angel-daemon games are a natural example of zero-sum games whose representation is naturally succinct. We show that the problems of deciding the existence of a pure Nash equilibrium or of a dominant strategy for a given player are ${\Sigma}^{p}_{2}$ -complete. Furthermore, computing the value of an angel-daemon game is EXP-complete. Thus, our results match the already known classification of the corresponding problems for the generic families of succinctly represented games with exponential number of actions.     

Processing peanuts and cottonseed

Two cases are presented to show how the elimination of bad operational habits and the use of controlling equipment can improve the efficiency of an oil mill. The cleaning of peanuts (farmer’s stock) is presented as an example of the need to use proper equipment for a given operation. A supply of good quality seed, together with the use of modern equipment, has improved the yields of oil and protein to the present values of 91% and 96% recovery, respectively. A growing fats and oils market in the Central American area and a limited supply of cottonseed are forcing the mills of Nicaragua to look for new oilseeds.     

A quantitative feedback solution to the multivariable tracking error problem

This paper introduces a novel solution for the multi‐input multi‐output (MIMO) quantitative feedback theory control design problem with tracking error specifications. Looking for a minimum controller overdesign, the technique finds new controller quantitative feedback theory bounds based on necessary and sufficient conditions for the existence of suitable associated prefilter matrix elements. It improves previous approaches to the subject and includes (i) the possibility of a free selection of the nominal plant, (ii) a less conservative application of the Schwartz inequality to decisively reduce the potential controller overdesign, (iii) a methodology to design independently the elements of the prefilter matrix, and (iv) a scope of application to both sequential and nonsequential MIMO controller design methods. The benefits of the new control design technique are illustrated by means of two examples. The first one, a standard 2 × 2 MIMO problem, is provided for comparison purposes with previous approaches. The second example, included as a major control challenge, deals with a well‐known demanding distillation column benchmark problem. Copyright © 2013 John Wiley & Sons, Ltd.     

Relation of swelling and Tg depression to the apparent free volume of a particle‐filled,epoxy‐based adhesive

The effect of hygrothermal aging on a particle‐filled, epoxy‐based adhesive was studied using a gravimetric sorption technique. This study has explored moisture sorption characteristics as well as the associated behaviors of swelling and the depression of the glass transition temperature (T_g). We observed that the diffusion of water in this adhesive has a non‐Fickian behavior, and the depression of T_g proceeds to a definite value that is independent of the final equilibrium water content of the system. Our observations suggest that water diffuses into the polymer in a dual‐sorption mode, in which water resides in two populations. In one population, water is considered to occupy apparent free volume of the adhesive, and the second population water infiltrates polymer structure and forms hydrogen‐bonded clusters. Our results show that hygrothermal aging temperature and swelling do not alter the apparent free volume of this adhesive. We conclude that the constant value of T_g depression at saturation implies that only water in the apparent free volume is responsible for the T_g depression, whereas the swelling proceeds through the formation of hydrogen bonds in the adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1436–1444, 2003     

A novel attractant for Mexican fruit fly,Anastrepha ludens,from fermented host fruit

Chemicals from fermented chapote fruit were identified and evaluated as attractants for hungry adult Mexican fruit flies in laboratory and greenhouse bioassays. Twenty-eight chemicals identified from an attractive gas-chromatography fraction were as attractive as a chapote volatiles extract (CV) when mixed in the same amounts found in CV. Sixteen of the chemicals were slightly attractive to flies when tested individually. A mixture containing 15 of the chemicals by design and the 16th as an impurity, in arbitrary concentrations, was at least as attractive as the original CV. In a series of experiments, the number of chemicals was reduced to three by elimination of unnecessary components. The three-component mixture retained the attractiveness of the 15-component mixture. The three chemicals were 1,8-cineole, ethyl hexanoate, and hexanol (CEH). Attractiveness of the three-chemical mixture was equal to the sum of the attractiveness of the three individual components, suggesting that each chemical binds to a different receptor type that independently elicits partial attraction behavior. Optimal ratios were 1011 of the three chemicals, respectively. Optimal test quantities ranged between 0.4–4g of 1,8-cineole and 40–400 ng each of ethyl hexanoate and hexanol applied to filter paper in the laboratory bioassays. A neat 1011 mixture of the chemicals was 1.8 times more attractive than aqueous solutions ofTorula dried yeast and borax to starved 2-day-old flies when the lures were tested in competing McPhail traps in a large greenhouse cage.Diptera: Tephritidae.     

Carbon nanotube supported ruthenium catalysts for the treatment of high strength wastewater with aniline using wet air oxidation

Multi-walled carbon nanotubes (MWCNT) can be efficiently used as support of ruthenium catalysts for the catalytic wet air oxidation of high strength wastewater containing aniline. Catalysts were prepared using different ruthenium precursors, Ruthenocene [Ru(η⁵-C₅H₅)₂], Ruthenium (1,5-cyclooctadiene, 1,3,5-cyclooctatriene) [Ru(cod)(cot)] and Ruthenium trichloride (RuCl₃ · xH₂O), different impregnation methods (excess solution and incipient wetness impregnation) and different MWCNT support surface chemistry (nitric acid oxidized MWCNT-COOH and Na₂CO₃ ion exchanged MWCNT-COONa). The efficiency of the aniline removal obtained with the catalysts prepared with different precursors decreases in the order [Ru(cod)(cot)] > RuCl₃ · xH₂O > [Ru(η⁵-C₅H₅)₂], 100% aniline conversion being obtained after 45 min of reaction with the catalyst prepared with [Ru(cod)(cot)]. The influence of the impregnation technique was found to be negligible, while the use of the MWCNT-COONa support led to increased catalyst performances when compared to that obtained with catalysts prepared with the MWCNT-COOH support. Leaching of ruthenium was observed in all cases, but the use of the precursor [Ru(cod)(cot)] and of the support MWCNT-COONa in the preparation of the catalysts seems to improve their stability. A direct relationship between metal load and catalyst stability was found and attributed to the strength of metal-support interactions.     

CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004