Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis

(Chemical Equation Presented) The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C-O bond scission, C-C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transi-tion- state rate constants for every elementary reaction and every pathway were calculated within 298-1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667-1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C-O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C-C bond scission. This C-O bond scission mechanism starts with breaking of C1-O5 and C6-O1 bonds with formation of CO molecule (C1-O1) simultaneously. C-C bond scission mechanism is the highest energetic barrier pathway for LG decomposition. © 2013 Elsevier Ltd. All rights reserved.

Interactions between pyrazole derived enantiomers and Chiralcel OJ: Prediction of enantiomer absolute configurations and elution order by molecular dynamics simulations

The separation of enantiomers and confirmation of their absolute configurations is significant in the development of chiral drugs. The interactions between the enantiomers of chiral pyrazole derivative and polysaccharide-based chiral stationary phase cellulose tris(4-methylbenzoate) (Chiralcel OJ) in seven solvents and under different temperature were studied using molecular dynamics simulations. The results show that solvent effect has remarkable influence on the interactions. Structure analysis discloses that the different interactions between two isomers and chiral stationary phase are dependent on the nature of solvents, which may invert the elution order. The computational method in the present study can be used to predict the elution order and the absolute configurations of enantiomers in HPLC separations and therefore would be valuable in development of chiral drugs.

Développement d’une méthode de simulation multi-échelle pour l’étude des grandes transformations dans les protéines

Les films de simulations qui accompagnent le document ont été réalisés avec Pymol.

Studies on the dynamics and rheology of dilute suspensions of Brownian particles in simple shear flow under the action of an external force

We present a novel approach to computing the orientation moments and rheological properties of a dilute suspension of spheroids in a simple shear flow at arbitrary Peclct number based on a generalised Langevin equation method. This method differs from the diffusion equation method which is commonly used to model similar systems in that the actual equations of motion for the orientations of the individual particles are used in the computations, instead of a solution of the diffusion equation of the system. It also differs from the method of 'Brownian dynamics simulations' in that the equations used for the simulations are deterministic differential equations even in the presence of noise, and not stochastic differential equations as in Brownian dynamics simulations. One advantage of the present approach over the Fokker-Planck equation formalism is that it employs a common strategy that can be applied across a wide range of shear and diffusion parameters. Also, since deterministic differential equations are easier to simulate than stochastic differential equations, the Langevin equation method presented in this work is more efficient and less computationally intensive than Brownian dynamics simulations.We derive the Langevin equations governing the orientations of the particles in the suspension and evolve a procedure for obtaining the equation of motion for any orientation moment. A computational technique is described for simulating the orientation moments dynamically from a set of time-averaged Langevin equations, which can be used to obtain the moments when the governing equations are harder to solve analytically. The results obtained using this method are in good agreement with those available in the literature.The above computational method is also used to investigate the effect of rotational Brownian motion on the rheology of the suspension under the action of an external force field. The force field is assumed to be either constant or periodic. In the case of con- I stant external fields earlier results in the literature are reproduced, while for the case of periodic forcing certain parametric regimes corresponding to weak Brownian diffusion are identified where the rheological parameters evolve chaotically and settle onto a low dimensional attractor. The response of the system to variations in the magnitude and orientation of the force field and strength of diffusion is also analyzed through numerical experiments. It is also demonstrated that the aperiodic behaviour exhibited by the system could not have been picked up by the diffusion equation approach as presently used in the literature.The main contributions of this work include the preparation of the basic framework for applying the Langevin method to standard flow problems, quantification of rotary Brownian effects by using the new method, the paired-moment scheme for computing the moments and its use in solving an otherwise intractable problem especially in the limit of small Brownian motion where the problem becomes singular, and a demonstration of how systems governed by a Fokker-Planck equation can be explored for possible chaotic behaviour.

Die aeroelastische Stabilitätsanalyse – ein praxisnaher Ansatz zur intervalltheoretischen Betrachtung von Modellierungsunsicherheiten am Flugzeug

Die Untersuchung des dynamischen aeroelastischen Stabilitätsverhaltens von Flugzeugen erfordert sehr komplexe Rechenmodelle, welche die wesentlichen elastomechanischen und instationären aerodynamischen Eigenschaften der Konstruktion wiedergeben sollen. Bei der Modellbildung müssen einerseits Vereinfachungen und Idealisierungen im Rahmen der Anwendung der Finite Elemente Methode und der aerodynamischen Theorie vorgenommen werden, deren Auswirkungen auf das Simulationsergebnis zu bewerten sind. Andererseits können die strukturdynamischen Kenngrößen durch den Standschwingungsversuch identifiziert werden, wobei die Ergebnisse Messungenauigkeiten enthalten. Für eine robuste Flatteruntersuchung müssen die identifizierten Unwägbarkeiten in allen Prozessschritten über die Festlegung von unteren und oberen Schranken konservativ ermittelt werden, um für alle Flugzustände eine ausreichende Flatterstabilität sicherzustellen. Zu diesem Zweck wird in der vorliegenden Arbeit ein Rechenverfahren entwickelt, welches die klassische Flatteranalyse mit den Methoden der Fuzzy- und Intervallarithmetik verbindet. Dabei werden die Flatterbewegungsgleichungen als parameterabhängiges nichtlineares Eigenwertproblem formuliert. Die Änderung der komplexen Eigenlösung infolge eines veränderlichen Einflussparameters wird mit der Methode der numerischen Fortsetzung ausgehend von der nominalen Startlösung verfolgt. Ein modifizierter Newton-Iterations-Algorithmus kommt zur Anwendung. Als Ergebnis liegen die berechneten aeroelastischen Dämpfungs- und Frequenzverläufe in Abhängigkeit von der Fluggeschwindigkeit mit Unschärfebändern vor.

Analysis and Simulation of Transverse Random Fracture of Long Fibre Reinforced Composites

La present tesi proposa una metodología per a la simulació probabilística de la fallada de la matriu en materials compòsits reforçats amb fibres de carboni, basant-se en l'anàlisi de la distribució aleatòria de les fibres. En els primers capítols es revisa l'estat de l'art sobre modelització matemàtica de materials aleatoris, càlcul de propietats efectives i criteris de fallada transversal en materials compòsits. El primer pas en la metodologia proposada és la definició de la determinació del tamany mínim d'un Element de Volum Representatiu Estadístic (SRVE) . Aquesta determinació es du a terme analitzant el volum de fibra, les propietats elàstiques efectives, la condició de Hill, els estadístics de les components de tensió i defromació, la funció de densitat de probabilitat i les funcions estadístiques de distància entre fibres de models d'elements de la microestructura, de diferent tamany. Un cop s'ha determinat aquest tamany mínim, es comparen un model periòdic i un model aleatori, per constatar la magnitud de les diferències que s'hi observen. Es defineix, també, una metodologia per a l'anàlisi estadístic de la distribució de la fibra en el compòsit, a partir d'imatges digitals de la secció transversal. Aquest anàlisi s'aplica a quatre materials diferents. Finalment, es proposa un mètode computacional de dues escales per a simular la fallada transversal de làmines unidireccionals, que permet obtenir funcions de densitat de probabilitat per a les variables mecàniques. Es descriuen algunes aplicacions i possibilitats d'aquest mètode i es comparen els resultats obtinguts de la simulació amb valors experimentals.

A cell by cell anisotropic adaptive mesh ALE scheme for the numerical solution of the Euler equations

In this paper a cell by cell anisotropic adaptive mesh technique is added to an existing staggered mesh Lagrange plus remap finite element ALE code for the solution of the Euler equations. The quadrilateral finite elements may be subdivided isotropically or anisotropically and a hierarchical data structure is employed. An efficient computational method is proposed, which only solves on the finest level of resolution that exists for each part of the domain with disjoint or hanging nodes being used at resolution transitions. The Lagrangian, equipotential mesh relaxation and advection (solution remapping) steps are generalised so that they may be applied on the dynamic mesh. It is shown that for a radial Sod problem and a two-dimensional Riemann problem the anisotropic adaptive mesh method runs over eight times faster.

National and sub-national assessments of soil organic carbon stocks and changes: The GEFSOC modelling system

Soil organic carbon (SOC) plays a vital role in ecosystem function, determining soil fertility, water holding capacity and susceptibility to land degradation. In addition, SOC is related to atmospheric CO, levels with soils having the potential for C release or sequestration, depending on land use, land management and climate. The United Nations Convention on Climate Change and its Kyoto Protocol, and other United Nations Conventions to Combat Desertification and on Biodiversity all recognize the importance of SOC and point to the need for quantification of SOC stocks and changes. An understanding of SOC stocks and changes at the national and regional scale is necessary to further our understanding of the global C cycle, to assess the responses of terrestrial ecosystems to climate change and to aid policy makers in making land use/management decisions. Several studies have considered SOC stocks at the plot scale, but these are site specific and of limited value in making inferences about larger areas. Some studies have used empirical methods to estimate SOC stocks and changes at the regional scale, but such studies are limited in their ability to project future changes, and most have been carried out using temperate data sets. The computational method outlined by the Intergovernmental Panel on Climate Change (IPCC) has been used to estimate SOC stock changes at the regional scale in several studies, including a recent study considering five contrasting eco regions. This 'one step' approach fails to account for the dynamic manner in which SOC changes are likely to occur following changes in land use and land management. A dynamic modelling approach allows estimates to be made in a manner that accounts for the underlying processes leading to SOC change. Ecosystem models, designed for site scale applications can be linked to spatial databases, giving spatially explicit results that allow geographic areas of change in SOC stocks to be identified. Some studies have used variations on this approach to estimate SOC stock changes at the sub-national and national scale for areas of the USA and Europe and at the watershed scale for areas of Mexico and Cuba. However, a need remained for a national and regional scale, spatially explicit system that is generically applicable and can be applied to as wide a range of soil types, climates and land uses as possible. The Global Environment Facility Soil Organic Carbon (GEFSOC) Modelling System was developed in response to this need. The GEFSOC system allows estimates of SOC stocks and changes to be made for diverse conditions, providing essential information for countries wishing to take part in an emerging C market, and bringing us closer to an understanding of the future role of soils in the global C cycle. (C) 2007 Elsevier B.V. All rights reserved.

Sequentially testing for a gene-drug interaction in a genomewide analysis

Assaying a large number of genetic markers from patients in clinical trials is now possible in order to tailor drugs with respect to efficacy. The statistical methodology for analysing such massive data sets is challenging. The most popular type of statistical analysis is to use a univariate test for each genetic marker, once all the data from a clinical study have been collected. This paper presents a sequential method for conducting an omnibus test for detecting gene-drug interactions across the genome, thus allowing informed decisions at the earliest opportunity and overcoming the multiple testing problems from conducting many univariate tests. We first propose an omnibus test for a fixed sample size. This test is based on combining F-statistics that test for an interaction between treatment and the individual single nucleotide polymorphism (SNP). As SNPs tend to be correlated, we use permutations to calculate a global p-value. We extend our omnibus test to the sequential case. In order to control the type I error rate, we propose a sequential method that uses permutations to obtain the stopping boundaries. The results of a simulation study show that the sequential permutation method is more powerful than alternative sequential methods that control the type I error rate, such as the inverse-normal method. The proposed method is flexible as we do not need to assume a mode of inheritance and can also adjust for confounding factors. An application to real clinical data illustrates that the method is computationally feasible for a large number of SNPs. Copyright (c) 2007 John Wiley & Sons, Ltd.

Structure-based energetics of protein interfaces guides foot-and-mouth disease virus vaccine design

Virus capsids are primed for disassembly, yet capsid integrity is key to generating a protective immune response. Foot-and-mouth disease virus (FMDV) capsids comprise identical pentameric protein subunits held together by tenuous noncovalent interactions and are often unstable. Chemically inactivated or recombinant empty capsids, which could form the basis of future vaccines, are even less stable than live virus. Here we devised a computational method to assess the relative stability of protein-protein interfaces and used it to design improved candidate vaccines for two poorly stable, but globally important, serotypes of FMDV: O and SAT2. We used a restrained molecular dynamics strategy to rank mutations predicted to strengthen the pentamer interfaces and applied the results to produce stabilized capsids. Structural analyses and stability assays confirmed the predictions, and vaccinated animals generated improved neutralizing-antibody responses to stabilized particles compared to parental viruses and wild-type capsids.

The Bullough-Dodd model coupled to matter fields

The Bullough-Dodd model is an important two-dimensional integrable field theory which finds applications in physics and geometry. We consider a conformally invariant extension of it, and study its integrability properties using a zero curvature condition based on the twisted Kac-Moody algebra A(2)((2)). The one- and two-soliton solutions as well as the breathers are constructed explicitly. We also consider integrable extensions of the Bullough-Dodd model by the introduction of spinor (matter) fields. The resulting theories are conformally invariant and present local internal symmetries. All the one-soliton solutions, for two examples of those models, are constructed using a hybrid of the dressing and Hirota methods. One model is of particular interest because it presents a confinement mechanism for a given conserved charge inside the solitons. (C) 2008 Elsevier B.V. All rights reserved.

Desenvolvimento de um sistema Inteligente para a análise de cartas dinamométricas no método de elevação por bombeio mecânico

The artificial lifting of oil is needed when the pressure of the reservoir is not high enough so that the fluid contained in it can reach the surface spontaneously. Thus the increase in energy supplies artificial or additional fluid integral to the well to come to the surface. The rod pump is the artificial lift method most used in the world and the dynamometer card (surface and down-hole) is the best tool for the analysis of a well equipped with such method. A computational method using Artificial Neural Networks MLP was and developed using pre-established patterns, based on its geometry, the downhole card are used for training the network and then the network provides the knowledge for classification of new cards, allows the fails diagnose in the system and operation conditions of the lifting system. These routines could be integrated to a supervisory system that collects the cards to be analyzed

Application of fuzzy logic for the evaluation of livestock slaughtering

A lógica fuzzy admite infinitos valores lógicos intermediários entre o falso e o verdadeiro. Com esse princípio, foi elaborado neste trabalho um sistema baseado em regras fuzzy, que indicam o índice de massa corporal de animais ruminantes com objetivo de obter o melhor momento para o abate. O sistema fuzzy desenvolvido teve como entradas as variáveis massa e altura, e a saída um novo índice de massa corporal, denominado Índice de Massa Corporal Fuzzy (IMC Fuzzy), que poderá servir como um sistema de detecção do momento de abate de bovinos, comparando-os entre si através das variáveis linguísticas )Muito BaixaM, ,BaixaB, ,MédiaM, ,AltaA e Muito AltaM. Para a demonstração e aplicação da utilização deste sistema fuzzy, foi feita uma análise de 147 vacas da raça Nelore, determinando os valores do IMC Fuzzy para cada animal e indicando a situação de massa corpórea de todo o rebanho. A validação realizada do sistema foi baseado em uma análise estatística, utilizando o coeficiente de correlação de Pearson 0,923, representando alta correlação positiva e indicando que o método proposto está adequado. Desta forma, o presente método possibilita a avaliação do rebanho, comparando cada animal do rebanho com seus pares do grupo, fornecendo desta forma um método quantitativo de tomada de decisão para o pecuarista. Também é possível concluir que o presente trabalho estabeleceu um método computacional baseado na lógica fuzzy capaz de imitar parte do raciocínio humano e interpretar o índice de massa corporal de qualquer tipo de espécie bovina e em qualquer região do País.

Análise da influência dos diferentes tempos de polimerização por luz incandescente sobre a resistência ao desgaste abrasivo de resinas compostas

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

Efeitos da adição de átomos de Mn na rede do GaN via métodos de estrutura eletrônica

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