The preparation and thermal decomposition of solid state compounds of 4-dimethylaminobenzylidenepyruvate and trivalent lanthanides and yttrium

Solid state Ln-DMBP compounds, where Ln represents trivalent lanthanides (except for promethium) and yttrium, and DMBP is 4-dimethylaminobenzylidenepyruvate, were prepared. Thermogravimetry (TG), differential thermal analysis (DTA), and other methods of analysis were used to characterize and to study the thermal stability and thermal decomposition of these compounds. © 1993.

Photocatalytic decomposition of rhodamine-b using scandium and silver-modified TiO2 powders

Semiconductor-mediated photocatalytic oxidation is an interesting method for water decontamination and a specially modified TiO2 is said to be a promising material. This study verified that the synthesis of 1wt%Ag modified-Sc0.01Ti0.99O1.995 powder samples prepared by Polymeric Precursor Method is capable of forming a mixture of anatase-rutile phase with high photocatalytic performance. This kind of material is found to have a lower bandgap compared to the TiO2-anatase commercial powders, which can be associated to an innovative hybrid modification. The simultaneous insertion of scandium in order to generate a p-type semiconductor and a metallic silver nanophase acting as an electron trapper demonstrated being capable of enhancing the degradation of rhodamine B compared to the commercial TiO2. In spite of the different thermal treatments or phase amounts, the hybrid modified powder samples showed higher photocatalytic activity than the commercial ones.

Invasive Litter, Not an Invasive Insectivore, Determines Invertebrate Communities in Hawaiian Forests

In Hawaii, invasive plants have the ability to alter litter-based food chains because they often have litter traits that differ from native species. Additionally, abundant invasive predators, especially those representing new trophic levels, can reduce prey. The relative importance of these two processes on the litter invertebrate community in Hawaii is important, because they could affect the large number of endemic and endangered invertebrates. We determined the relative importance of litter resources, represented by leaf litter of two trees, an invasive nitrogen-fixer, Falcataria moluccana, and a native tree, Metrosideros polymorpha, and predation of an invasive terrestrial frog, Eleutherodactylus coqui, on leaf litter invertebrate abundance and composition. Principle component analysis revealed that F. moluccana litter creates an invertebrate community that greatly differs from that found in M. polymorpha litter. We found that F. moluccana increased the abundance of non-native fragmenters (Amphipoda and Isopoda) by 400% and non-native predaceous ants (Hymenoptera: Formicidae) by 200%. E. coqui had less effect on the litter invertebrate community; it reduced microbivores by 40% in F. moluccana and non-native ants by 30% across litter types. E. coqui stomach contents were similar in abundance and composition in both litter treatments, despite dramatic differences in the invertebrate community. Additionally, our results suggest that invertebrate community differences between litter types did not cascade to influence E. coqui growth or survivorship. In conclusion, it appears that an invasive nitrogen-fixing tree species has a greater influence on litter invertebrate community abundance and composition than the invasive predator, E. coqui.

Morphological patterns and community organization in leaf-litter ant assemblages

We present a new approach to determine the number and composition of guilds, using the hyperdiverse leaf-litter ant fauna as a model, based on appropriate morphological variables and species co-occurrence null models to describe the complex assemblages of interacting Species Community structure at the 1-m(2) scale. We obtained 18 linear morphometric measures from 949 workers of 171 leaf-litter ant species (18762 measurements) surveyed in four Atlantic Forest localities to test whether the assemblages are morphologically structured; the morphological characters were selected to indicate diet and foraging habits. Principal components analysis was used to characterize the morphospace and to describe the guild structure (number of species and composition). The guild proportionality assembly rule (significant tendency toward constant proportion of species in guilds) was assessed at the 1-m(2) scale. Our analysis indicates that the division of leaf-litter ants into guilds is based mainly on microhabitat distribution in the leaf-litter, body size and shape, eye size, and phylogeny. The same guild scheme applied to four more sites shows that different Atlantic Forest areas have the same leaf-fitter ant guilds. The guild proportionality assembly rule was confirmed for most guilds, Suggesting that there are guild-specific limitations on species coexistence within assemblages; on the other hand, in a few cases the variance in guild proportion was greater than expected under the null assumptions. Other studies on ant functional group classification are partially supported by our quantitative morphological analysis. Our results, however, imply that there are more compartments than indicated in previous models, particularly among cryptic species (confined to soil and litter) and tropical climate specialists. We argue that a general null model for the analysis of species association based oil morphology can reveal objectively defined groups and may thus contribute to a robust theory to explain community structure in general and have important consequences on studies of litter ant community ecology in particular.

Assembly of Myrmelachista Roger (Formicidae: Formicinae) in twigs fallen on the leaf litter of Brazilian Atlantic Forest

The nests of Myrmelachista are found in tree trunk cavities and branches. The biology of these arboreal ants is still relatively unknown. We investigated the nesting behaviour of this genus in fallen dry twigs in the Atlantic rainforest of southeastern Brazil. Physical characteristics of the nests, colony demographics, presence of breeders and ant worker sizes were recorded. Samples were collected weekly for 12 months, along open, sunny and undisturbed trails within forest remnants. In all, 202 nests were collected and six species were recorded. Myrmelachista ruszkii had the highest population of immatures and the greatest number of nests found. Myrmelachista nodigera had the smallest workers, was the least populous and the colony was housed in the finest branches. These results expand the current knowledge about the diversity and biology of Myrmelachista in the Brazilian Atlantic forest, and describe polydomic nests and competitive behaviour of M. ruszkii.

Characterization of depolymerized residues from extremely low acid hydrolysis (ELA) of sugarcane bagasse cellulose: Effects of degree of polymerization, crystallinity and crystallite size on thermal decomposition

Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H2SO4 at 190, 210 and 225 degrees C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225 degrees C for 80,40 and 8 min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210 degrees C were similar to that of Avicel. (C) 2011 Elsevier B.V. All rights reserved.

The sigma-isotypic decomposition and the sigma-index of reversible-equivariant systems

This work is concerned with dynamical systems in presence of symmetries and reversing symmetries. We describe a construction process of subspaces that are invariant by linear Gamma-reversible-equivariant mappings, where Gamma is the compact Lie group of all the symmetries and reversing symmetries of such systems. These subspaces are the sigma-isotypic components, first introduced by Lamb and Roberts in (1999) [10] and that correspond to the isotypic components for purely equivariant systems. In addition, by representation theory methods derived from the topological structure of the group Gamma, two algebraic formulae are established for the computation of the sigma-index of a closed subgroup of Gamma. The results obtained here are to be applied to general reversible-equivariant systems, but are of particular interest for the more subtle of the two possible cases, namely the non-self-dual case. Some examples are presented. (C) 2011 Elsevier BM. All rights reserved.

Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides

The chemiluminescence of cyclic peroxides activated by oxidizable fluorescent dyes is an example of chemically initiated electron exchange luminescence (CIEEL), which has been used also to explain the efficient bioluminescence of fireflies. Diphenoyl peroxide and dimethyl-1,2-dioxetanone were used as model compounds for the development of this CIEEL mechanism. However, the chemiexcitation efficiency of diphenoyl peroxide was found to be much lower than originally described. In this work, we redetermine the chemiexcitation quantum efficiency of dimethyl-1,2-dioxetanone, a more adequate model for firefly bioluminescence, and found a singlet quantum yield (Phi(s)) of 0.1%, a value at least 2 orders of magnitude lower than previously reported. Furthermore, we synthesized two other 1,2-dioxetanone derivatives and confirm the low chemiexcitation efficiency (Phi(s) < 0.1%) of the intermolecular CIEEL-activated decomposition of this class of cyclic. peroxides. These results are compared with other chemiluminescent reactions, supporting the general trend that intermolecular CIEEL systems are much less efficient in generating singlet excited states than analogous intramolecular processes (Phi(s) approximate to 50%), with the notable exception of the peroxyoxalate reaction (Phi(s) approximate to 60%).

Thermal decomposition kinetics of Brazilian limestones: effect of CO2 partial pressure

The influence of the partial pressure of carbon dioxide (CO2) on the thermal decomposition process of a calcite (CI) and a dolomite (DP) is investigated in this paper using a thermogravimetric analyser. The tests were non-isothermal at five different heating rates in dynamic atmosphere of air with 0% and 15% carbon dioxide (CO2). In the atmosphere without CO2, the average activation energies (E-alpha) were 197.4 kJ mol(-1) and 188.1 kJ mol(-1) for CI and DP, respectively. For the DP with 15% CO2, two decomposition steps were observed, indicating a change of mechanism. The values of E-alpha for 15% CO2 were 378.7 kJ mol(-1) for the CI, and 299.8 kJ mol(-1) (first decomposition) and 453.4 kJ mol(-1) (second decomposition) for the DP, showing that the determination of E-alpha for DP should in this case be considered separately in those two distinct regions. The results obtained in this study are relevant to understanding the behaviour changes in the thermal decomposition of limestones with CO2 partial pressure when applied to technologies, such as carbon capture and storage (CCS), in which carbon dioxide is present in high concentrations.

Kinetics of thermal decomposition of niobium hydride

High-purity niobium powders can be obtained from the well-known hydride-dehydride (HDH) process. The aim of this work was the investigation of the structural phase transition of the niobium hydride to niobium metal as function of temperature, heating rate and time. The niobium powder used in this work was obtained by high-temperature hydriding of niobium machining chips followed by conventional ball milling and sieving. X-ray diffraction measurements were carried out in vacuum using a high-temperature chamber coupled to an X-ray diffractometer. During the dehydriding process, it is possible to follow the phase transition from niobium hydride to niobium metal starting at about 380 degrees C for a heating rate of 20 degrees C/min. The heating rate was found to be an important parameter, since complete dehydriding was obtained at 490 degrees C for a heating rate of 20 degrees C/min. The higher dehydriding rate was found at 500 degrees C. Results contribute to a better understanding of the kinetics of thermal decomposition of niobium hydride to niobium metal. (C) 2011 Elsevier Ltd. All rights reserved.

A novel method for power quality multiple disturbance decomposition based on Independent Component Analysis

In this paper, a novel method for power quality signal decomposition is proposed based on Independent Component Analysis (ICA). This method aims to decompose the power system signal (voltage or current) into components that can provide more specific information about the different disturbances which are occurring simultaneously during a multiple disturbance situation. The ICA is originally a multichannel technique. However, the method proposes its use to blindly separate out disturbances existing in a single measured signal (single channel). Therefore, a preprocessing step for the ICA is proposed using a filter bank. The proposed method was applied to synthetic data, simulated data, as well as actual power system signals, showing a very good performance. A comparison with the decomposition provided by the Discrete Wavelet Transform shows that the proposed method presented better decoupling for the analyzed data. (C) 2012 Elsevier Ltd. All rights reserved.

Development of Plurimetallic Electrocatalysts Prepared by Decomposition of Polymeric Precursors for EtOH/O-2 Fuel Cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal: carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Evaluating links through spectral decomposition

Spectral decomposition has rarely been used to investigate complex networks. In this work we apply this concept in order to define two kinds of link-directed attacks while quantifying their respective effects on the topology. Several other kinds of more traditional attacks are also adopted and compared. These attacks had substantially diverse effects, depending on each specific network (models and real-world structures). It is also shown that the spectrally based attacks have special effects in affecting the transitivity of the networks.