Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. All rights reserved.

As técnicas NASVD e MNF e sua aplicação na redução de ruídos em dados gamaespectrométricos

A desintegração radioativa é um processo aleatório e a estimativa de todas as medidas associadas é governada por leis estatísticas. Os perfis de taxas de contagem são sempre "ruidosos" quando utilizados períodos curtos como um segundo para cada medida. Os filtros utilizados e posteriormente as correções feitas no processamento atual de dados gamaespectrométricos não são suficientes para remover ou diminuir, consideravelmente, o ruído oriundo do espectro. Dois métodos estatísticos que atuam diretamente nos dados coletados, isto é, nos espectros, vêm sendo sugeridos na literatura para remover e minimizar estes ruídos remanescentes o Noise-Adjusted Singular Value Decomposition - NASVD e Maximum Noise Fraction - MNF. Estes métodos produzem uma redução no ruído de forma significativa. Neste trabalho eles foram implementados dentro do ambiente de processamento do software Oasis Montaj e aplicados na área compreendida pelos blocos I e II do levantamento aerogeofísico que recobre a porção oeste da Província Mineral do Tapajós, entre os Estados do Pará e Amazonas. Os dados filtrados e não-filtrados com as técnicas de NASVD e MNF foram processados com os parâmetros e constantes fornecidos pela empresa Lasa Engenharia e Prospecções S.A., sendo estes comparados. Os resultados da comparação entre perfis e mapas apresentaram-se de forma promissora, pois houve um ganho na resolução dos produtos.

Termogravimetria: um novo enfoque para a clássica determinação de cálcio em cascas de ovos

The use of thermoanalytical data in sample preparation is described as a tool to catch the students' attention to some details that can simplify both the analysis and the analytical procedure. In this case, the thermal decomposition of eggshells was first investigated by thermogravimetry (TGA). Although the classical procedures suggest long exposure to high temperatures, the TGA data showed that the decomposition of organic matter takes place immediately when the sample is heated up to 800 °C under air atmosphere. After decomposition, the calcium content was determined by flame atomic emission photometry and compared with the results obtained using classical volumetric titration with EDTA.

Síntese, caracterização e análise térmica dos sais de lítio, sódio e potássio do ácido palmítico e do seu éster etílico

Alkaline salts of the palmitic acid were synthesized and characterized from aqueous and ethanolic medium. The salts were characterized by elemental analysis (EA) and infrared spectroscopy (IR). EA and IR, being its synthesis comproved, also characterized the ethyl palmitate. All the salts and the ester were submitted to thermal analysis using thermogravimetry (TG), and differential thermal analysis (DTA) in the temperature ranging from room to 700 ºC under air dynamic atmosphere. Differential scanning calorimetry (DSC) measurements were taken from -90 ºC up to temperatures close to the starting of the decomposition temperature, determined by thermogravimetry, using heating and cooling cycles.

Estudos termoanalíticos de sais de sódio e potássio de ditiocarbamatos em atmosfera oxidante

Thermoanalytical behavior of sodium and potassium salts of pyrrolidinedithiocarbamate (pyr), piperidineditiocarbamate (pip), morpholinedithiocarbamate (mor), hexametileneiminedithiocarbamate (hex), were investigated. In a first step the salts were synthesized and characterized by infrared spectroscopy (FTIR), ¹H and 13C nuclear magnetic resonance (NMR) and elementar analysis. Finally, thermal analytical (TG/DTG and DSC) studies were performed in order to evaluate the thermal stability, as well as the pathways of the thermal decomposition based in the intermediate and final decomposition products.

Design, construction and evaluation of a simple pressurized solvent extraction system

This work describes the construction and testing of a simple pressurized solvent extraction (PSE) system. A mixture of acetone:water (80:20), 80 ºC and 103.5 bar, was used to extract two herbicides (Diuron and Bromacil) from a sample of polluted soil, followed by identification and quantification by high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). The system was also used to extract soybean oil (70 ºC and 69 bar) using pentane. The extracted oil was weighed and characterized through the fatty acid methyl ester analysis (myristic (< 0.3%), palmitic (16.3%), stearic (2.8%), oleic (24.5%), linoleic (46.3%), linolenic (9.6%), araquidic (0.3%), gadoleic (< 0.3%), and behenic (0.3%) acids) using high-resolution gas chromatography with flame ionization detection (HRGC-FID). PSE results were compared with those obtained using classical procedures: Soxhlet extraction for the soybean oil and solid-liquid extraction followed by solid-phase extraction (SLE-SPE) for the herbicides. The results showed: 21.25 ± 0.36% (m/m) of oil in the soybeans using the PSE system and 21.55 ± 0.65% (m/m) using the soxhlet extraction system; extraction efficiency (recovery) of herbicides Diuron and Bromacil of 88.7 ± 4.5% and 106.6 ± 8.1%, respectively, using the PSE system, and 96.8 ± 1.0% and 94.2 ± 3.9%, respectively, with the SLP-SPE system; limit of detection (LOD) and limit of quantification (LOQ) for Diuron of 0.012 mg kg-1 and 0.040 mg kg-1, respectively; LOD and LOQ for Bromacil of 0.025 mg kg-1 and 0.083 mg kg-1, respectively. The linearity used ranged from 0.04 to 1.50 mg L-1 for Diuron and from 0.08 to 1.50 mg L-1 for Bromacil. In conclusion, using the PSE system, due to high pressure and temperature, it is possible to make efficient, fast extractions with reduced solvent consumption in an inert atmosphere, which prevents sample and analyte decomposition.

Estudo da decomposição térmica de propelente sólido compósito de baixa emissão de fumaça

The thermal decomposition of hydroxyl-terminated polybutadiene (HTPB)/ammonium nitrate (AN) based propellants, so called smokeless formulations, and raw materials were investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The thermoanalytical profile of different components and of propellant were evaluated and the Arrhenius parameters for the thermal decomposition of the propellant sample were determined by the Ozawa method. The kinetic parameters of the thermal decomposition of propellant samples were determined by DSC measurements. The values obtained for activation energy (Ea) and pre-exponential factor were 163 kJ mol-1 and 1.94x10(6) min-1.

Luz: um raro produto de reação

The production of visible light by chemical reactions constitutes interesting and fascinating phenomena and several reaction mechanisms are discussed to rationalize excited state formation. Most efficient chemiluminescence reactions are thought to involve one or more electron transfer steps and chemiexcitation is believed to occur by radical annihilation. A brief introduction to the general principles of light production and the main known chemiexcitation mechanisms will be given here. Subsequently, recent results on the mechanistic elucidation of efficient chemiluminescence systems, as the peroxyoxalate reaction, the induced decomposition of phenoxy-substituted 1,2-dioxetanes and the catalyzed decomposition of new a-peroxylactones will be discussed.

Chaotic Patterns in Aeroelastic Signals

This work presents the analysis of nonlinear aeroelastic time series from wing vibrations due to airflow separation during wind tunnel experiments. Surrogate data method is used to justify the application of nonlinear time series analysis to the aeroelastic system, after rejecting the chance for nonstationarity. The singular value decomposition (SVD) approach is used to reconstruct the state space, reducing noise from the aeroelastic time series. Direct analysis of reconstructed trajectories in the state space and the determination of Poincare sections have been employed to investigate complex dynamics and chaotic patterns. With the reconstructed state spaces, qualitative analyses may be done, and the attractors evolutions with parametric variation are presented. Overall results reveal complex system dynamics associated with highly separated flow effects together with nonlinear coupling between aeroelastic modes. Bifurcations to the nonlinear aeroelastic system are observed for two investigations, that is, considering oscillations-induced aeroelastic evolutions with varying freestream speed, and aeroelastic evolutions at constant freestream speed and varying oscillations. Finally, Lyapunov exponent calculation is proceeded in order to infer on chaotic behavior. Poincare mappings also suggest bifurcations and chaos, reinforced by the attainment of maximum positive Lyapunov exponents. Copyright (C) 2009 F. D. Marques and R. M. G. Vasconcellos.

The CoRoT-7 planetary system: two orbiting super-Earths

We report on an intensive observational campaign carried out with HARPS at the 3.6 m telescope at La Silla on the star CoRoT-7. Additional simultaneous photometric measurements carried out with the Euler Swiss telescope have demonstrated that the observed radial velocity variations are dominated by rotational modulation from cool spots on the stellar surface. Several approaches were used to extract the radial velocity signal of the planet(s) from the stellar activity signal. First, a simple pre-whitening procedure was employed to find and subsequently remove periodic signals from the complex frequency structure of the radial velocity data. The dominant frequency in the power spectrum was found at 23 days, which corresponds to the rotation period of CoRoT-7. The 0.8535 day period of CoRoT-7b planetary candidate was detected with an amplitude of 3.3 m s(-1). Most other frequencies, some with amplitudes larger than the CoRoT-7b signal, are most likely associated with activity. A second approach used harmonic decomposition of the rotational period and up to the first three harmonics to filter out the activity signal from radial velocity variations caused by orbiting planets. After correcting the radial velocity data for activity, two periodic signals are detected: the CoRoT-7b transit period and a second one with a period of 3.69 days and an amplitude of 4 m s(-1). This second signal was also found in the pre-whitening analysis. We attribute the second signal to a second, more remote planet CoRoT-7c. The orbital solution of both planets is compatible with circular orbits. The mass of CoRoT-7b is 4.8 +/- 0.8 (M(circle plus)) and that of CoRoT-7c is 8.4 +/- 0.9 (M(circle plus)), assuming both planets are on coplanar orbits. We also investigated the false positive scenario of a blend by a faint stellar binary, and this may be rejected by the stability of the bisector on a nightly scale. According to their masses both planets belong to the super-Earth planet category. The average density of CoRoT-7b is rho = 5.6 +/- 1.3 g cm(-3), similar to the Earth. The CoRoT-7 planetary system provides us with the first insight into the physical nature of short period super-Earth planets recently detected by radial velocity surveys. These planets may be denser than Neptune and therefore likely made of rocks like the Earth, or a mix of water ice and rocks.

PARTITIONED ANALYSIS FOR DIMENSIONALLY-HETEROGENEOUS HYDRAULIC NETWORKS

In this work an iterative strategy is developed to tackle the problem of coupling dimensionally-heterogeneous models in the context of fluid mechanics. The procedure proposed here makes use of a reinterpretation of the original problem as a nonlinear interface problem for which classical nonlinear solvers can be applied. Strong coupling of the partitions is achieved while dealing with different codes for each partition, each code in black-box mode. The main application for which this procedure is envisaged arises when modeling hydraulic networks in which complex and simple subsystems are treated using detailed and simplified models, correspondingly. The potentialities and the performance of the strategy are assessed through several examples involving transient flows and complex network configurations.

Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI center dot NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI center dot PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 degrees C, 200 degrees C and 250 degrees C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 degrees C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.

On quantum integrability of the Landau-Lifshitz model

We investigate the quantum integrability of the Landau-Lifshitz (LL) model and solve the long-standing problem of finding the local quantum Hamiltonian for the arbitrary n-particle sector. The particular difficulty of the LL model quantization, which arises due to the ill-defined operator product, is dealt with by simultaneously regularizing the operator product and constructing the self-adjoint extensions of a very particular structure. The diagonalizibility difficulties of the Hamiltonian of the LL model, due to the highly singular nature of the quantum-mechanical Hamiltonian, are also resolved in our method for the arbitrary n-particle sector. We explicitly demonstrate the consistency of our construction with the quantum inverse scattering method due to Sklyanin [Lett. Math. Phys. 15, 357 (1988)] and give a prescription to systematically construct the general solution, which explains and generalizes the puzzling results of Sklyanin for the particular two-particle sector case. Moreover, we demonstrate the S-matrix factorization and show that it is a consequence of the discontinuity conditions on the functions involved in the construction of the self-adjoint extensions.

DNA damage by sulfite autoxidation catalyzed by cobalt complexes

DNA damage was investigated in the presence of sulfite, dissolved oxygen and cobalt(II) complexes with glycylglycylhistidine, glycylhistidyllysine, glycylglycyltyrosylarginine and tetraglycine. These studies indicated that only Co(II) complexed with glycylglycylhistidine (GGH) induced DNA strand breaks at low sulfite concentrations (1-80 mu M) via strong oxidants formed in the reaction. In the presence of the other complexes, some damage occurred only in the presence of high sulfite concentrations (0.1-2.0 mM) after incubation for 4 h. In the presence of GGH, Co(II) and dissolved O(2), DNA damage must involve a reactive high-valent cobalt complex. The damaging effect was increased by adding S(IV), due to the oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by the complex. SO(3)(center dot)-S-, HO(center dot) and H(center dot) radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline N-oxide). The results indicate that Co(II) binds O2 in the presence of GGH, and leads to the formation of a DMPO-HO(center dot) adduct without first forming free superoxide or hydroxyl radical, supporting the participation of a reactive high-valent cobalt complex.

Chemiluminescence-based uphill energy conversion

The conversion of red excitation light into blue emission light (uphill energy conversion) using unstable 1,2-dioxetanes is described. The method is based on 1,2-dioxetane formation by red-light sensitized photooxygenation of adequate alkenes and subsequent blue-light emission due to thermal 1,2-dioxetane cleavage. The energy gain resulting from the chemical energy obtained in the transformation of an alkene into two carbonyl compounds transforms a red-light excitation laser beam into a blue-light chemiluminescence emission, producing thereby a formal anti-Stokes shift of 200-250 nm, opening up a whole spectrum of possible applications.