The use of acids,niobium oxide,and zeolite catalysts for esterification reactions

We have evaluated the influence of alcohol/fatty acid molar ratio (methanol or ethanol), water and catalyst concentrations and temperature by the esterification of palm fatty acids by heterogeneous acid catalysts (varying types, forms, and particle size). Polynaphtalene sulfonic acid (PSA) and niobium oxide (Nb₂O₅) presented better performance than zeolite catalysts. Reaction with methanol presented higher conversion than with ethanol. The experimental design showed that the most relevant variable is the catalyst concentration and all interactions become important in process. A heterogeneous kinetic model was proposed and applied to experimental data. One of the models was adequate for methanol reaction, whereas the homogeneous model was more appropriate for ethanol reaction. Copyright © 2009 John Wiley & Sons, Ltd.     

Comparison between Berkovich,Vickers and conical indentation tests: A three-dimensional numerical simulation study

Three-dimensional numerical simulations of Berkovich, Vickers and conical indenter hardness tests were carried out to investigate the influence of indenter geometry on indentation test results of bulk and composite film/substrate materials. The strain distributions obtained from the three indenters tested were studied, in order to clarify the differences in the load–indentation depth curves and hardness values of both types of materials. For bulk materials, the differentiation between the results obtained with the three indenters is material sensitive. The indenter geometry shape factor, β, for evaluating Young’s modulus for each indenter, was also estimated. Depending on the indenter geometry, distinct mechanical behaviours are observed for composite materials, which are related to the size of the indentation region in the film. The indentation depth at which the substrate starts to deform plastically is sensitive to indenter geometry.     

On the application of TRIMAP to problems with multiple decision makers

In this paper the potentialities of TRIMAP to provide decision support in multiobjective problems with multiple decision makers are exploited. TRIMAP is an interactive three-objective linear programming package which enables a progressive and selective learning of the nondominated solution set. The aim is to aid the opposing parties in exploring their own preferences and to explore the dynamic nature of the negotiation process.     

Use of olefin templates in queued chemical transformations using late transition metal catalysis. Total synthesis of cis and trans bupleurynol via a single multireaction sequence

1-Bromo-2-iodoethylene (9) was used as a central, pseudosymmetric building block for the fully convergent and modular synthesis of two related natural products, cis (1a) and trans (1b) bupleurynol. In doing so, a 9-step synthesis of 1a (reported previously) has been vastly truncated to one single operation by using queued cross-coupling reactions with Pd catalysis, negating the need for any protecting group chemistry.     

Identification of lectin activity in the hemolymph ofCastnia licus Drury,a sugar-cane giant borer (Lepidoptera-Castniidae)

Castnia licus Drury, in the larvae stage, is a major pest in the sugarcane industry of Northeastern Brazil (giant borer). A natural hemagglutination activity was detected in the larvae hemolymph of this insect and the activity have not been inhibited by tested carbohydrates. Fractionation with ammonium sulfate showed that the supernatant of the 15–30% fraction (S15-30%) had the lectin’s highest specific activity. Acidic and basic lectin activities were separated by chromatography on CM-cellulose; the fractionated molecular forms showed distinct electrophoresis mobilities.     

Dead Ends and Detours En Route to Total Syntheses of the 1990s A list of abbreviations can be found at the end of the article

From the very beginning organic chemistry and total synthesis have been intimately joined. In fact, one of the first things that freshmen in organic chemistry learn is how to join two molecules together to obtain a more complex one. Of course they still have a long way to go to become fully mature synthetic chemists, but they must have the primary instinct to build molecules, as synthesis is the essence of organic chemistry. With the different points of view that actually coexist in the chemical community about the maturity of the science (art, or both) of organic synthesis, it is clear that nowadays we know how to make almost all of the most complex molecules ever isolated. The primary question is how easy is it to accomplish? For the readers of papers describing the total synthesis of either simple or complex molecules, it appears that the routes followed are, most of the time, smooth and free of troubles. The synthetic scheme written on paper is, apparently, done in the laboratory with few, if any, modifications and these, essentially, seem to be based on finding the optimal experimental conditions to effect the desired reaction. Failures in the planned synthetic scheme to achieve the goal, detours imposed by unexpected reactivity, or the absence of reactivity are almost never discussed, since they may diminish the value of the work reported. This review attempts to look at total synthesis from a different side; it will focus on troubles found during the synthetic work that cause detours from the original synthetic plan, or on the dead ends that eventually may force redesign. From there, the evolution from the original route to the final successful one that achieves the synthetic target will be presented. The syntheses discussed in this paper have been selected because they contain explicit information about the failures of the original synthetic plan, together with the evolution of the final route to the target molecule. Therefore, they contain a lot of useful negative information that may otherwise be lost.     

Stability of multi-server polling system with server limits

We consider a multi-server polling system with server limits, that is the number of servers that can attend a queue simultaneously is limited. Stability conditions are available when service policies are unlimited. The definition of stability conditions when both server limits and limited service policies apply remains an open problem. We postulate a conjecture for the stability condition in this case that is supported by our simulation results. The study of this particular variant of the multi-server polling system is motivated by the performance evaluation of next generation passive optical access networks.     

The effect of tannins on Mediterranean ruminant ingestive behavior: the role of the oral cavity

Sheep, cattle and goat are domestic ruminants of significant economic interest in the Mediterranean region. Although sharing the same pasture ranges, they ingest different plants and plant parts and, consequently different levels of tannins. This suggests an ability to detect and adapt ingestion according to animal physiological limits of tolerance for plant secondary metabolites. This review will detail the effects of dietary tannins on feeding behavior, and the role of the oral cavity in this process, with focus on such ruminant species. The role of salivary protein profile in tannin perception in the oral cavity, and as a defense mechanism, will be discussed.     

Electron transfer-induced fragmentation of thymine and uracil in atom-molecule collisions

Ion-pair formation has been studied in hyperthermal (30-100 eV) neutral potassium collisions with gas phase thymine (C(5)H(6)N(2)O(2)) and uracil (C(4)H(4)N(2)O(2)). Negative ions formed by electron transfer from the alkali atom to the target molecule were analysed by time-of-flight (TOF) mass spectrometry. The most abundant product anions are assigned to CNO(-) and (U-H)(-)/(T-H)(-) and the associated electron transfer mechanisms are discussed. Special emphasis is given to the enhancement of ring breaking pathways in the present experiments, notably CNO(-) formation, compared with free electron attachment measurements.     

Improved Solvent‐Free Dakin Oxidation Protocol

A solvent‐free Dakin reaction with mCPBA was accomplished with various aromatic aldehydes, resulting in an easy and improved methodology for the preparation of corresponding phenols. 3,4‐Methylenedioxyphenol, 3,4‐dimethoxyphenol, 4‐methoxyphenol, 4‐chlorophenol, and other functionalized phenols were obtained in high yields from the corresponding aromatic aldehydes in a few minutes. This new methodology represents an efficient alternative for this important synthetic conversion.