Shvo's catalyst in chemoenzymatic dynamic kinetic resolution of amines-inner or outer sphere mechanism?

Evidence is provided for the inner-sphere mechanism with actual metal coordination of the racemic amine in the crucial hydrogen transfer step promoted by Shvo's catalyst of the chemoenzymatic dynamic kinetic resolution (DKR) of amines. Key intermediates involved in this H-transfer step were intercepted and continuously monitored by electrospray ionization mass spectrometry (ESI-MS) and characterized by their dissociation chemistries via ESI-MS/MS. © 2013 The Royal Society of Chemistry.

Síntese enantiosseletiva de beta-aminoésteres quirais através de sistemas enzimáticos envolvendo transaminases

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Three-Dimensional Semiautomatic Road Extraction From a High-Resolution Aerial Image by Dynamic-Programming Optimization in the Object Space

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Monitoring of cure kinetic prepreg and cure cycle modeling

Cure kinetic model is an integral part of composite process simulation, which is used to predict the degree of curing and the amount of the generated heat. The parameters involved in kinetic models are usually determined empirically from isothermal or dynamic differential scanning calorimetry (DSC) data. In this work, DSC and rheological techniques were used to investigate some of the kinetic parameters of cure reactions of carbon/F161 epoxy prepreg and to evaluate the cure cycle used to manufacture polymeric composites for aeronautical applications. As a result, it was observed that the F161 prepreg presents cure kinetic with total order 1.2-1.9. (c) 2006 Springer Science + Business Media, Inc.

On the dynamic behaviour of the "click" mechanism in dipteran flight

In this paper, the dynamic behaviour of the "click" mechanism is analysed. A more accurate model is used than in the past, in which the limits of movement due to the geometry of the flight mechanism are imposed. Moreover, the effects of different damping models are investigated. In previous work, the damping model was assumed to be of the linear viscous type for simplicity, but it is likely that the damping due to drag forces is nonlinear. Accordingly, a model of damping in which the damping force is proportional to the square of the velocity is used, and the results are compared with the simpler model of linear viscous damping. Because of the complexity of the model an analytical approach is not possible so the problem has been cast in terms of non-dimensional variables and solved numerically. The peak kinetic energy of the wing root per energy input in one cycle is chosen to study the effectiveness of the "click" mechanism compared with a linear resonant mechanism. It is shown that, the "click" mechanism has distinct advantages when it is driven below its resonant frequency. When the damping is quadratic, there are some further advantages compared to when the damping is linear and viscous, provided that the amplitude of the excitation force is large enough to avoid the erratic behaviour of the mechanism that occurs for small forces. (C) 2011 Elsevier Ltd. All rights reserved.

The structure of a native L-amino acid oxidase, the major component of the Vipera ammodytes ammodytes venomic, reveals dynamic active site and quaternary structure stabilization by divalent ions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Kinetic model of poly(3-hydroxybutyrate) thermal degradation from experimental non-isothermal data

The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

Thermal degradation of a composite solid propellant examined by DSC - Kinetic study

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius Parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 W mol(-1), the pre-exponential factor, A, was 2.04.10(10) min(-1) and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here.

Kinetic evaluation of the pyrolysis of high density polyethylene over H-AlMCM-41 material

The AlMCM-41 material with Si/Al=50 was synthesized by hydrothermal method, using cethyltrimethylammonium as template. The protonic H-AlMCM-41 acid form was obtained by ion exchange with ammonium chloride solution and subsequent calcination. The characterization of the material by several techniques showed that a good-quality MCM-41 material was obtained. High-density polyethylene (HDPE) has been submitted to thermal degradation alone, and in presence of the exchanged H-AlMCM-41 catalyst at a concentration of 1: 1 in mass (H-AlMCM-41/HDPE). The reactor was connected on line to a gas chromatograph connected to a mass spectrometer. This process was evaluated by thermogravimetry (TG), from 350 to 600degreesC, under helium dynamic atmosphere, with heating rates of 5.0; 10.0 and 20.0 degreesC/min. From TG curves, the activation energy, calculated using a multiple heating rate integral kinetic method, decreased from 225.5 KJ.mol(-1), for the pure polymer (HDPE), to 184.7 KJ.mol(-1), in the presence of the catalyst (H-AlMCM-41/HDPE).

Kinetic parameters of polymer degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

Determination of Total Sulfur in Agricultural Samples by High-Resolution Continuum Source Flame Molecular Absorption Spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dynamic programming approach for road centerline extraction from digital images

This paper presents a dynamic programming approach for semi-automated road extraction from medium-and high-resolution images. This method is a modified version of a pre-existing dynamic programming method for road extraction from low-resolution images. The basic assumption of this pre-existing method is that roads manifest as lines in low-resolution images (pixel footprint> 2 m) and as such can be modeled and extracted as linear features. On the other hand, roads manifest as ribbon features in medium- and high-resolution images (pixel footprint ≤ 2 m) and, as a result, the focus of road extraction becomes the road centerlines. The original method can not accurately extract road centerlines from medium- and high- resolution images. In view of this, we propose a modification of the merit function of the original approach, which is carried out by a constraint function embedding road edge properties. Experimental results demonstrated the modified algorithm's potential in extracting road centerlines from medium- and high-resolution images.

Dynamic analysis of a new piezoelectric flextensional actuator using the J1-J4 optical interferometric method

Piezoelectric actuators are widely used in positioning systems which demand high resolution such as scanning microscopy, fast mirror scanners, vibration cancellation, cell manipulation, etc. In this work a piezoelectric flextensional actuator (PFA), designed with the topology optimization method, is experimentally characterized by the measurement of its nanometric displacements using a Michelson interferometer. Because this detection process is non-linear, adequate techniques must be applied to obtain a linear relationship between an output electrical signal and the induced optical phase shift. Ideally, the bias phase shift in the interferometer should remain constant, but in practice it suffers from fading. The J1-J4 spectral analysis method provides a linear and direct measurement of dynamic phase shift in a no-feedback and no-phase bias optical homodyne interferometer. PFA application such as micromanipulation in biotechnology demands fast and precise movements. So, in order to operate with arbitrary control signals the PFA must have frequency bandwidth of several kHz. However as the natural frequencies of the PFA are low, unwanted dynamics of the structure are often a problem, especially for scanning motion, but also if trajectories have to be followed with high velocities, because of the tracking error phenomenon. So the PFA must be designed in such a manner that the first mechanical resonance occurs far beyond this band. Thus it is important to know all the PFA resonance frequencies. In this work the linearity and frequency response of the PFA are evaluated up to 50 kHz using optical interferometry and the J1-J4 method.

Simulation of dynamic pinion course using Runge-Kutta's method and impact modeling

Once defined the relationship between the Starter Motor components and their functions, it is possible to develop a mathematical model capable to predict the Starter behavior during operation. One important aspect is the engagement system behavior. The development of a mathematical tool capable of predicting it is a valuable step in order to reduce the design time, cost and engineering efforts. A mathematical model, represented by differential equations, can be developed using physics laws, evaluating force balance and energy flow through the systems degrees of freedom. Another important physical aspect to be considered in this modeling is the impact conditions (particularly on the pinion and ring-gear contact). This work is a report of those equations application on available mathematical software and the resolution of those equations by Runge-Kutta's numerical integration method, in order to build an accessible engineering tool. Copyright © 2011 SAE International.

Carbon nanotubes/polyamide 6.6 nanostructured composites crystallization kinetic study

Compared with the traditional composites, the incorporation of carbon nanotubes into polymeric matrices can generate materials with superior properties, especially thermal, electrical and tribological properties. The aim of this study was to study the polyamide 6.6/carbon nanotubes (PA 6.6/CNT) nanostructured composites crystallization kinetics. The solution mixing technique was used to obtain the nanostructured composites studied in this work. PA 6.6 films were produced with amounts of 0.1, 0.5, and 1.0 wt% (weight/weight) CNT. X-ray diffraction analyses were performed in order to determine the crystallographic properties of nanostructured composite. The nanostructured composites crystallization kinetic study was performed using the differential scanning calorimetry under isothermal and nonisothermal (dynamic) conditions. The results have shown addition of CNTs in the PA 6.6 reduces the Avrami exponent, affecting the crystallization process of the composite. © The Author(s) 2012.