Acidolysis of babassu fat catalyzed by immobilized lipase

The lipase-catalyzed interesterification of oils and fats gives products that are unobtainable by chemical interesterification methods. Acidolysis of babassu fat and palmitic acid, catalyzed by immobilized lipase (Lipozyme; Novo Industri, Bagsveard, Denmark), was studied. The reactions were performed at 65°C with 5% w/w enzyme for 4 h. The molar proportions of babassu fat/palmitic acid were 1∶0.1, 1∶0.3 and 1∶0.5. At the end of the reaction period, the catalyst particles were removed by filtration, and the residual oil was extracted with organic solvent (diethyl ether). The recovered particles were then reused. The palmitic acid content of babassu fat before and after acidolysis changed from 10 to 22% at a molar proportion of 1∶0.5. The equilibrium was attained in about 4 h. The original water and enzymatic activities of Lipozyme were maintained after acidolysis. Water sorption isotherms of the immobilized enzyme were determined at 25, 35 and 45°C. From the temperature dependence of the isotherms, isosteric heats of sorption were evaluated by means of the Clausius Clapeyron equation. Monolayer moisture content was calculated by means of the B.E.T. and Guggenhein-Anderson-De Boer analyses. Paper presented at the International Meeting on Fats and Oils Technology, Universidade Estadual de Campinas, Brazil, 1991.     

Inductive Model Generation for Text Classification Using a Bipartite Heterogeneous Network

Algorithms for numeric data classification have been applied for text classification. Usually the vector space model is used to represent text collections. The characteristics of this representation such as sparsity and high dimensionality sometimes impair the quality of general-purpose classifiers. Networks can be used to represent text collections, avoiding the high sparsity and allowing to model relationships among different objects that compose a text collection. Such network- based representations can improve the quality of the classification results. One of the simplest ways to represent textual collections by a network is through a bipartite heterogeneous network, which is composed of objects that represent the documents connected to objects that represent the terms. Heterogeneous bipartite networks do not require computation of similarities or relations among the objects and can be used to model any type of text collection. Due to the advantages of representing text collections through bipartite heterogeneous networks, in this article we present a text classifier which builds a classification model using the structure of a bipartite heterogeneous network. Such an algorithm, referred to as IMBHN （Inductive Model Based on Bipartite Heterogeneous Network）, induces a classification model assigning weights to objects that represent the terms for each class of the text collection. An empirical evaluation using a large amount of text collections from different domains shows that the proposed IMBHN algorithm produces significantly better results than k-NN, C4.5, SVM, and Naive Bayes algorithms.     

Degradation of Leaf Litter Phenolics by Aquatic and Terrestrial Isopods

To investigate species-specific decomposition rates of litter from native (Quercus faginea) and introduced (Eucalyptus globulus) tree species in Portugal, we monitored changes in the phenolic signature of leaf litter during decomposition as mediated by an aquatic, Proasellus coxalis (Isopoda: Asellota), and two terrestrial, Porcellio dispar and Eluma caelatum (Isopoda: Oniscidea), detritivores. Although the litter of Eucalyptus and Quercus did not differ in overall protein precipitation capacity, we detected differences in terms of contents of particular phenolic compounds and phenol oxidation products. Accordingly, we observed food-specific consumption rates in Proasellus, but not in the terrestrial isopods. Proasellus digested Eucalyptus at significantly higher rates than Quercus, whereas the opposite was the case for Eluma, and Porcellio digested both litter types equally well. Despite slight differences in detail, effects of Proasellus on changes in the signature of litter phenolics were similar for both litter types, whereas terrestrial isopods—Porcellio and Eluma, although they differed from each other—digestively degraded phenolic compounds in Eucalyptus and Quercus litter, respectively, in different ways. Overall, however, degradation of litter phenolics was similarly effective on both litter types. From these data, we conclude that decomposition of Eucalyptus litter does not proceed more slowly than of litter from native Portuguese trees.     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Study of the thermomechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work describes the preparation and characterization of composite materials obtained by the combination of natural rubber (NR) and carbon black (CB) in different percentages, aiming to improve their mechanical properties, processability, and electrical conductivity, aiming future applications as transducer in pressure sensors. The composites NR/CB were characterized through optical microscopy (OM), DC conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA), and stress–strain test. The electrical conductivity varied between 10^?9 and 10 S m^?1, depending on the percentage of CB in the composite. Furthermore, a linear (and reversible) dependence of the conductivity on the applied pressure between 0 and 1.6 MPa was observed for the sample with containing 80 wt % of NR and 20% of CB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The cationic polymerization of α-methylstyrene in liquid sulfur dioxide initiated by the HI/I2 system

The polymerization of α-methylstyrene (αMeSty) initiated by HI/I₂ or HI in the presence of liquid sulfur dioxide has been investigated. The number-average molecular weight increased with the monomer concentration for reactions initiated by the HI/I₂ system. I₂ also participates in the initiation process, increasing the number-average polymer chain at higher monomer concentration. HI alone is also able to initiate the polymerization of αMeSty in the presence of SO₂. With this initiator, transfer reaction can be minimized in systems containing low amount of SO₂. Received: 19 December 1996/Revised: 27 January 1997/Accepted 29 January 1997     

The effect of H2 treatment on the activity of activated carbon for the oxidation of organic contaminants in water and the H2O2 decomposition

In this work, hydrogen peroxide reactions, i.e. H₂O₂ decomposition and oxidation of organics in aqueous medium, were studied in the presence of activated carbon. It was observed that the carbon pre-treatment with H₂ at 300, 500, 700 and 800 °C resulted in an increase in activity for both reactions. The carbons were characterized by BET nitrogen adsorption, thermogravimetric analyses (TG), temperature programmed reduction (TPR), electron paramagnetic resonance (EPR), iodometric titration and determination of the acid/basic sites. TPR experiments showed that activated carbon reacts with H₂ at temperatures higher than 400 °C. The treatment produces a slight increase in the surface area. EPR analyses indicate the absence of unpaired electrons in the carbon. Iodometric titrations and TG analyses suggested that the treatment with H₂ generates reduction sites in the carbon structure, with concentration of approximately 0.33, 0.53, 0.59, 0.65 and 0.60 mmol/g for carbons treated at 25, 300, 500, 700 and 800 °C, respectively. It was also observed the appearance of basic sites which might be related to the reduction sites. It is proposed that these reducing sites in the carbon can activate H₂O₂ to generate HO^* radicals which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water.     

Model falsification using set‐valued observers for a class of discrete‐time dynamic systems: a coprime factorization approach

This article introduces a new method for model falsification using set‐valued observers, which can be applied to a class of discrete linear time‐invariant dynamic systems with time‐varying model uncertainties. In comparison with previous results, the main advantages of this approach are as follows: The computation of the convex hull of the set‐valued estimates of the state can be avoided under certain circumstances; to guarantee convergence of the set‐valued estimates of the state, the required number of previous steps is at most as large as the number of states of the nominal plant; and it provides a straightforward nonconservative method to falsify uncertain models of dynamic systems, including open‐loop unstable plants. The results obtained are illustrated in simulation, emphasizing the advantages and shortcomings of the suggested method. Copyright © 2013 John Wiley & Sons, Ltd.     

Relationship between crystalline structure and mechanical behavior in isotropic and oriented polyamide 6

Polyamide 6 (PA6) isotropic films and oriented cables were prepared by compression molding or by consecutive extrusion and cold‐drawing. These samples were isothermally annealed in the 120–200°C range and were then subjected to tensile tests at room temperature. Synchrotron wide‐angle X‐ray scattering (WAXS) and small‐angle X‐ray scattering (SAXS) patterns were obtained before and after mechanical failure. These data were related with the mechanical properties of the respective PA6 samples. The annealing of isotropic PA6 resulted in an increase in the Young's modulus (E) and yield stress (σ_y) values, which was attributed to the observed proportional reduction of the d‐spacings of the intersheet distances in both the α‐PA6 and γ‐PA6 polymorphs. Analysis of the WAXS and SAXS patterns of isotropic PA6 after break allowed the supposition of structural changes in the amorphous phase, with these being better pronounced with increasing annealing temperature; this made the samples less ductile. In oriented PA6 samples, annealing resulted in a drastic increase in the E and σ_y values accompanied by a phase transition from γ‐PA6 to α‐PA6 and a well‐pronounced reduction in the intersheet distances of both polymorphs. The stretching of the oriented samples led to an additional γ‐to‐α transition, whose extent was also related to structural changes in the amorphous phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2242–2252, 2007