Bayesian L-optimal exact design of experiments for biological kinetic models

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

DNA hybridization mechanism in an interfacial environment: What hides beneath first order k (s(-1)) kinetic constant?

The scientific question addressed in this work is: what hides beneath first order kinetic constant k (s(-1)) measured for hybridization of a DNA target on a biosensor surface. Kinetics hybridization curves were established with a 27 MHz quartz microbalance (9 MHz, third harmonic) biosensor, constituted of a 20-base probe monolayer deposited on a gold covered quartz surface. Kinetics analysis, by a known two-step adsorption-hybridization mechanism, is well appropriate to fit properly hybridization kinetics curves, for complementary 20-base to 40-base targets over two concentration decades. It was found that the K-1 (M-1) adsorption constant, relevant to the first step, concerns an equilibrium between non hybridized targets and hybridized pre-complex and increases with DNA target length. It was established that k(2) (s(-1)), relevant to irreversible formation of a stable duplex, varies in an opposite way to K-1 with DNA target length. (C) 2012 Published by Elsevier B.V.

A joint theoretical and kinetic investigation on the fragmentation of (N-halo)-2-amino cycloalkanecarboxylates

A combined theoretical and experimental study to elucidate the molecular mechanism for the Grob fragmentation of different (N-halo)-2-amino cyclocarboxylates with the nitrogen atom in exocyclic position: (N-Cl)-2-amino cyclopropanecarboxylate (1), (N-Cl)-2-amino cyclobutanecarboxylate (2), (N-Cl)-2-amino cyclopentanecarboxylate (3) and (N-Cl)-2-amino cyclohexanecarboxylate (4), and the corresponding acyclic compounds, (N-Cl)-2-amino isobutyric acid (A), (N-Cl)-2-amino butyric acid (B), has been carried out. The kinetics of decomposition for these compounds and related bromine derivatives were experimentally determined by conventional and stopped-flow UV spectrophotometry. The reaction products have been analyzed by GC and spectrophotometry. Theoretical analysis is based in the localization of stationary points (reactants and transition structures) on the potential energy surface. Calculations were carried out at B3LYP/6-31+G* and MP2/6-31+G* computing methods in the gas phase, while solvent effects have been included by means the self-consistent reaction field theory, PCM continuum model, at MP2/6-31+G* and MP4/6-31+G*//MP2/6-31+G* calculation levels. Based on both experimental and theoretical results, the different Grob fragmentation processes show a global synchronicity index close to 0.9, corresponding to a nearly concerted process. At the TSs, the N-Cl bond breaking is more advanced than the C-C cleavage process. An antiperiplanar configuration of these bonds is reached at the TSs, and this geometrical arrangement is the key factor governing the decomposition. In the case of 1 and 2 the ring strain prevents this spatial disposition, leading to a larger value of the activation barrier. Natural population analysis shows that the polarization of the N-Cl and C-C bonds along the bond-breaking process can be considered the driving force for the decomposition and that a negative charge flows from the carboxylate group to the chlorine atom to assist the reaction pathway. A comparison of theoretical and experimental results shows the relevance of calculation level and the inclusion of solvent effects for determining accurate unimolecular rate coefficients for the decomposition process. © 2002 Published by Elsevier Science B.V.

Cytogenetic analysis in the spermatogenesis of Triatoma melanosoma (Reduviidae; Heteroptera)

Triatomines are of great concern in public health because they are vectors of Chagas' disease. This study presents an analysis of the species Triatoma melanosoma. The cytogenetic characteristics of triatomines include holocentric chromosomes, post-reductional meiosis in the sex chromosomes and nucleolar fragmentation in the meiotic cycle. The methodology utilized consisted of the techniques of lacto-acetic orcein staining and silver ion impregnation. The organs analyzed were adult testicles. The results enabled to classify the chromosomes by number and size, being three large, eight medium and one small heterochromosome. The three largest chromosomes and the heterochromosomes showed heteropyknotic chromatin in meiosis. The heterochromosomes in 8.05% of the cells in metaphase I behaved as pseudobivalents, contrasting with 91.95% of the cells with individualized sex chromosomes, confirming the achiasmatic nature of these chromosomes. However, the pseudobivalents occurred prominently in metaphase II (78.38%), this fact probably is related to the post-reductional nature of the sex chromosomes. The nucleolus in T. melanosoma persisted until the diplotene phase after which it began to fragment. Nucleolar corpuscles were observed in metaphases I and II and during anaphases I and II, these characteristics being related to the phenomenon of nucleolar persistence. In the initial spermatids, peripheral silver ion impregnation occurred, which could be analogous to the pre-nucleolar corpuscles observed after fragmentation. Thus, this study extends our knowledge of the characteristics of triatomines, in particular, heteropyknotic degree, kinetic activity, formation of sex chromosome achiasmatic pseudobivalency, confirmation of the fragmentation phenomenon, and post-meiotic nucleolar reactivation. ©FUNPEC-RP.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

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.

Kinetic parameters for thermal decomposition of hydrazine

The propulsion of most of the operating satellites comprises monopropellant (hydrazine - N2H4) or bipropellant (monometilydrazine - MMH and nitrogen tetroxide) chemical systems. When some sample of the propellant tested fails, the entire sample lot shall be rejected, and this action has turned into a health problem due to the high toxicity of N2H 4. Thus, it is interesting to know hydrazine thermal behavior in several storage conditions. The kinetic parameters for thermal decomposition of hydrazine in oxygen and nitrogen atmospheres were determined by Capela-Ribeiro nonlinear isoconversional method. From TG data at heating rates of 5, 10, and 20 C min-1, kinetic parameters could be determined in nitrogen (E = 47.3 ± 3.1 kJ mol-1, lnA = 14.2 ± 0.9 and T b = 69 C) and oxygen (E = 64.9 ± 8.6 kJ mol-1, lnA = 20.7 ± 3.1 and T b = 75 C) atmospheres. It was not possible to identify a specific kinetic model for hydrazine thermal decomposition due to high heterogeneity in reaction; however, experimental f(α)g(α) master-plot curves were closed to F 1/3 model. © 2013 Akadémiai Kiadó, Budapest, Hungary.

Kinetic study of pyrolysis of castor beans (Ricinuscommunis L) presscake: an alternative use for solid waste arising from the biodiesel production

This work investigated the effects of temperature and of rate of heating on the kinetic parameters of pyrolysis of castor beans presscake, a byproduct generated in the biodiesel production process. Pyrolysis process was investigated by thermogravimetric analysis, and parameters were obtained from nonisothermal experiments. The results obtained from the process of thermal decomposition indicated the elimination of humidity and the decomposition of organic components of the biomass. DTG curves showed that the heating rate affects the temperature of maximum decomposition of the material. Kinetic parameters such as activation energy and pre-exponential factor were obtained by model-free methods proposed by Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), and Kissinger. Experimental results showed that the kinetic parameters values of the FWO and KAS methods display good agreement and can be used to understand the mechanism of degradation of the cake. In a generalized way, the results contribute to better understanding of the processes of biomass pyrolysis.

Mathematical modeling and analysis of the flocculation process in chambers in series

In this study, the flocculation process in continuous systems with chambers in series was analyzed using the classical kinetic model of aggregation and break-up proposed by Argaman and Kaufman, which incorporates two main parameters: K (a) and K (b). Typical values for these parameters were used, i. e., K (a) = 3.68 x 10(-5)-1.83 x 10(-4) and K (b) = 1.83 x 10(-7)-2.30 x 10(-7) s(-1). The analysis consisted of performing simulations of system behavior under different operating conditions, including variations in the number of chambers used and the utilization of fixed or scaled velocity gradients in the units. The response variable analyzed in all simulations was the total retention time necessary to achieve a given flocculation efficiency, which was determined by means of conventional solution methods of nonlinear algebraic equations, corresponding to the material balances on the system. Values for the number of chambers ranging from 1 to 5, velocity gradients of 20-60 s(-1) and flocculation efficiencies of 50-90 % were adopted.

P-I class metalloproteinase from Bothrops moojeni venom is a post-proline cleaving peptidase with kininogenase activity: Insights into substrate selectivity and kinetic behavior

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Analysis of ibuprofen enantiomers in rat plasma by liquid chromatography with tandem mass spectrometry

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

Evaluation of Decomposition Kinetics of Poly (Ether-Ether-Ketone) by Thermogravimetric Analysis

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

Benzoxazine Resin/Carbon Nanotube Nanostructured Composite's Degradation Kinetic

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

Nonoxidative thermal degradation kinetic of polyamide 6,6 reinforced with carbon nanotubes

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

Quantitative phase analysis from X-ray diffraction in Y-TZP dental ceramics: A critical evaluation

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