Connections between Classical and Parametric Network Entropies

This paper explores relationships between classical and parametric measures of graph (or network) complexity. Classical measures are based on vertex decompositions induced by equivalence relations. Parametric measures, on the other hand, are constructed by using information functions to assign probabilities to the vertices. The inequalities established in this paper relating classical and parametric measures lay a foundation for systematic classification of entropy-based measures of graph complexity.

Palladium catalysed tandem cyclisation - Anion capture processes .2. Cyclisation onto alkynes or allenes with hydride capture.

A wide range of palladium catalysed regio- and stereo-specific 5-, 6- and 7-exo-dig mono-, bis- and tris-cyclisation processes of aryl and vinyl halides and allylic acetates are described. The mono- and bis-cyclisation processes terminate in hydride capture from piperidine-formic acid or sodium formate. Addition of TI2CO3 results in alkyne-allene isomerisation and leads, after cyclisation, to 1,3-dienes which give Diels-Alder adducts in good yield. Copyright (C) 1996 Elsevier Science Ltd

Enhanced medial-axis-based block-structured meshing in 2-D

New techniques are presented for using the medial axis to generate decompositions on which high quality block-structured meshes with well-placed mesh singularities can be generated. Established medial-axis-based meshing algorithms are effective for some geometries, but in general, they do not produce the most favourable decompositions, particularly when there are geometric concavities. This new approach uses both the topological and geometric information in the medial axis to establish a valid and effective arrangement of mesh singularities for any 2-D surface. It deals with concavities effectively and finds solutions that are most appropriate to the geometric shapes. Resulting meshes are shown for a number of example models.

Generating analysis topology using virtual topology operators

Virtual topology operations have been utilized to generate an analysis topology definition suitable for downstream mesh generation. Detailed descriptions are provided for virtual topology merge and split operations for all topological entities, where virtual decompositions are robustly linked to the underlying geometry. Current virtual topology technology is extended to allow the virtual partitioning of volume cells. A valid description of the topology, including relative orientations, is maintained which enables downstream interrogations to be performed on the analysis topology description, such as determining if a specific meshing strategy can be applied to the virtual volume cells. As the virtual representation is a true non-manifold description of the sub-divided domain the interfaces between cells are recorded automatically. Therefore, the advantages of non-manifold modelling are exploited within the manifold modelling environment of a major commercial CAD system without any adaptation of the underlying CAD model. A hierarchical virtual structure is maintained where virtual entities are merged or partitioned. This has a major benefit over existing solutions as the virtual dependencies here are stored in an open and accessible manner, providing the analyst with the freedom to create, modify and edit the analysis topology in any preferred sequence.

Supervised Aggregative Feature Extraction for Big Data Time Series Regression

In many applications, and especially those where batch processes are involved, a target scalar output of interest is often dependent on one or more time series of data. With the exponential growth in data logging in modern industries such time series are increasingly available for statistical modeling in soft sensing applications. In order to exploit time series data for predictive modelling, it is necessary to summarise the information they contain as a set of features to use as model regressors. Typically this is done in an unsupervised fashion using simple techniques such as computing statistical moments, principal components or wavelet decompositions, often leading to significant information loss and hence suboptimal predictive models. In this paper, a functional learning paradigm is exploited in a supervised fashion to derive continuous, smooth estimates of time series data (yielding aggregated local information), while simultaneously estimating a continuous shape function yielding optimal predictions. The proposed Supervised Aggregative Feature Extraction (SAFE) methodology can be extended to support nonlinear predictive models by embedding the functional learning framework in a Reproducing Kernel Hilbert Spaces setting. SAFE has a number of attractive features including closed form solution and the ability to explicitly incorporate first and second order derivative information. Using simulation studies and a practical semiconductor manufacturing case study we highlight the strengths of the new methodology with respect to standard unsupervised feature extraction approaches.

Eurozone Network Connectedness During Calm and Crisis: Evidence from the MTS Platform for Interdealer Trading of European Sovereign Debt

This paper examines the connectedness of the Eurozone sovereign debt market over the period 2005–2011. By employing measures built from the variance decompositions of approximating models we are able to define weighted, directed networks that enable a deeper understanding of the relationships between the Eurozone countries. We find that connectedness in the Eurozone was very high during the calm market conditions preceding the global financial crisis but decreased dramatically when the crisis took hold, and worsened as the Eurozone sovereign debt crisis emerged. The drop in connectedness was especially prevalent in the case of the peripheral countries with some of the most peripheral countries deteriorating into isolation. Our results have implications for both market participants and regulators.

Besov spaces and the Laplacian on fractal H-sets

Nesta tese são estudados espaços de Besov de suavidade generalizada em espaços euclidianos, numa classe de fractais designados conjuntos-h e em estruturas abstractas designadas por espaços-h. Foram obtidas caracterizações e propriedades para estes espaços de funções. Em particular, no caso de espaços de Besov em espaços euclidianos, foram obtidas caracterizações por diferenças e por decomposições em átomos não suaves, foi provada uma propriedade de homogeneidade e foram estudados multiplicadores pontuais. Para espaços de Besov em conjuntos-h foi obtida uma caracterização por decomposições em átomos não suaves e foi construído um operador extensão. Com o recurso a cartas, os resultados obtidos para estes espaços de funções em fractais foram aplicados para definir e trabalhar com espaços de Besov de suavidade generalizada em estruturas abstractas. Nesta tese foi também estudado o laplaciano fractal, considerado a actuar em espaços de Besov de suavidade generalizada em domínios que contêm um conjunto-h fractal. Foram obtidos resultados no contexto de teoria espectral para este operador e foi estudado, à custa deste operador, um problema de Dirichlet fractal no contexto de conjuntos-h.

Espectrometria de massa de macrociclos e dos seus aductos com o ADN

O trabalho de investigação desenvolvido teve como objectivo o estudo por espectrometria de massa com ionização por electrospray de compostos tetrapirrólicos (porfirinas e corróis) e das suas interacções com G-quadruplexes (estruturas de ADN de ordem superior, ricas em guanina). A química em fase gasosa de porfirinas catiónicas e neutras, e de corróis, foi investigada, tendo-se verificado a ocorrência de processos inesperados que foram objecto de um estudo aprofundado: redução das porfirinas catiónicas durante o processo global de electrospray e formação, na câmara de colisões, de aductos dos corróis com moléculas de água, ambos os processos detectados no modo de iões positivos. A redução das porfirinas ocorre através da formação de agregados catião-anião-solvente e catião-solvente-anião e os diferentes tipos de agregados conduzem a diferentes espécies reduzidas. A formação de aductos com água, bem como de outros iões-diagnóstico, permitiu a diferenciação dos isómeros posicionais dos corróis. Este último grupo de compostos foi igualmente estudado no modo de iões negativos. A espectrometria de massa com ionização por electrospray no modo de iões negativos foi também usada no estudo de aductos quadruplex-porfirina. Foi observada a formação de aductos do tipo [Q + nNH4+ + Pp+ -(z+n+p)H+ ]z- (Q=quadruplex, P=porfirina, p=0,1,2,3,4) para todas as porfirinas seleccionadas. A caracterização destes aductos foi efectuada através das suas decomposições induzidas por colisões. Verificou-se que o número de cargas presente nas porfirinas é um factor muito importante na estabilidade dos aductos formados, que aumenta com o aumento do número de cargas. O tipo e tamanho dos grupos substituintes presentes na porfirina não mostraram ter uma influência significativa nos processos de fragmentação. Os resultados obtidos apontam para uma ligação externa porfirina - G-quadruplex, com as porfirinas empilhadas nas extremidades dos quadruplexes.

A study of the thermal decomposition of allyl t-butyl peroxide and 3-hydroperoxy-1-propene (allyl hydroperoxide) in toluene /|nby Krishnankutty Nair V. G. -- 260 St. Catharines [Ont. : s. n.],

Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.

Task-Dependent Oscillatory Brain Activity During Oculomotor Delayed Response Task

This study used three Oculomotor Delayed Response (ODR) tasks to investigate the unique cognitive demands during the delay period. Changes in alpha power were used to index cognitive efforts during the delay period. Continuous EEGs from 25 healthy young adults (18-34 years) were recorded using dense electrode array. The data was analyzed by 6-cycle Morlet wavelet decompositions in the frequency range of 2-30 Hz to create time- frequency decompositions for four midline electrode sites. The 99% confidence intervals using the bootstrapped 20% trimmed mean of the 10 Hz frequency were used to examine the differences among conditions. Compared to two Memory conditions (Match and Non-Match), Control condition yielded significant differences in all frequencies over the entire trial period, suggesting a cognitive state difference. Compared to Match condition, the Non–Match condition had lower alpha activity during the delay period at each midline electrode site reflecting the higher cognitive effort required.

Half-sandwich Complexes of Ruthenium; Synthesis and Application to Catalysis

This thesis describes syntheses and catalytic reactivity of several half-sandwich complexes of ruthenium. The neutral ruthenium trihydride complex, Cp(PPri3)RuH3(1), can efficiently catalyse the H/D exchange reaction between various organic substrates and deuterium sources, such as benzene-d6. Moreover, the H/D exchange reactions of polar substrates were also observed in D2O, which is the most attractive deuterium source due to its low cost and low toxicity. Importantly, the H/D exchange under catalytic conditions was achieved not only in aromatic compounds but also in substituted liphatic compounds. Interestingly, in the case of alkanes and alkyl chains, highly selective deuterium incorporation in the terminal methyl positions was observed. It was discovered that the methylene units are engaged in exchange only if the molecule contains a donating functional group, such as O-and N-donors, C=C double bonds, arenes and CH3. The cationic half-sandwich ruthenium complex [Cp(PPri3)Ru(CH3CN)2]+(2) catalyses the chemoselective mono-addition of HSiMe2Ph to pyridine derivatives to selectively give the 1,4-regiospecific, N-silylated products. An ionic hydrosilylation mechanismis suggested based on the experiments. To support this mechanistic proposal, kinetic studies under catalytic conditions were performed. Also, the 1,4-regioselective mono-hydrosilylation of nitrogen containing compounds such as phenanthroline, quinoline and acridine can be achieved with the related Cp*complex [Cp*(phen)Ru(CH3CN)]+(3) (phen = 1,10-phenanthroline) and HSiMe2Ph under mild conditions. The cationic ruthenium complex 2 can also be used as an efficient catalyst for transfer hydrogenation of various organic substrates including carbonyls, imines, nitriles and esters. Secondary alcohols, amines, N-isopropylidene amines and ether compounds can be obtained in moderate to high yields. In addition, other ruthenium complexes, 1,3 and [Cp*(PPri3)Ru(CH3CN)2]+(4), can catalyse transfer hydrogenation of carbonyls although the reactions were sluggish compared to the ones of 2. The possible intermediate, Cp(PPri3)Ru(CH3CN)(H), was characterized by NMR at low temperature and the kinetic studies for the transfer hydrogenation of acetophenone were performed. Recently, chemoselective reduction of acid chlorides to aldehydes catalysed by the complex 2 was reported. To extend the catalytic reactivity of 2, reduction of iminoyl chlorides, which can be readily obtained from secondary amides, to the corresponding imines and aldehydes was investigated. Various substituted iminoyl chlorides were converted into the imines and aldehydes under mild conditions and several products were isolated with moderate yields.

Aversion Analysis

In this paper : a) the consumer’s problem is studied over two periods, the second one involving S states, and the consumer being endowed with S+1 incomes and having access to N financial assets; b) the consumer is then representable by a continuously differentiable system of demands, commodity demands, asset demands and desirabilities of incomes (the S+1 Lagrange multiplier of the S+1 constraints); c) the multipliers can be transformed into subjective Arrow prices; d) the effects of the various incomes on these Arrow prices decompose into a compensation effect (an Antonelli matrix) and a wealth effect; e) the Antonelli matrix has rank S-N, the dimension of incompleteness, if the consumer can financially adjust himself when facing income shocks; f) the matrix has rank S, if not; g) in the first case, the matrix represents a residual aversion; in the second case, a fundamental aversion; the difference between them is an aversion to illiquidity; this last relation corresponds to the Drèze-Modigliani decomposition (1972); h) the fundamental aversion decomposes also into an aversion to impatience and a risk aversion; i) the above decompositions span a third decomposition; if there exists a sure asset (to be defined, the usual definition being too specific), the fundamental aversion admits a three-component decomposition, an aversion to impatience, a residual aversion and an aversion to the illiquidity of risky assets; j) the formulas of the corresponding financial premiums are also presented.

Non-negative matrix decomposition approaches to frequency domain analysis of music audio signals

On étudie l’application des algorithmes de décomposition matricielles tel que la Factorisation Matricielle Non-négative (FMN), aux représentations fréquentielles de signaux audio musicaux. Ces algorithmes, dirigés par une fonction d’erreur de reconstruction, apprennent un ensemble de fonctions de base et un ensemble de coef- ficients correspondants qui approximent le signal d’entrée. On compare l’utilisation de trois fonctions d’erreur de reconstruction quand la FMN est appliquée à des gammes monophoniques et harmonisées: moindre carré, divergence Kullback-Leibler, et une mesure de divergence dépendente de la phase, introduite récemment. Des nouvelles méthodes pour interpréter les décompositions résultantes sont présentées et sont comparées aux méthodes utilisées précédemment qui nécessitent des connaissances du domaine acoustique. Finalement, on analyse la capacité de généralisation des fonctions de bases apprises par rapport à trois paramètres musicaux: l’amplitude, la durée et le type d’instrument. Pour ce faire, on introduit deux algorithmes d’étiquetage des fonctions de bases qui performent mieux que l’approche précédente dans la majorité de nos tests, la tâche d’instrument avec audio monophonique étant la seule exception importante.

Approches générales de résolution pour les problèmes multi-attributs de tournées de véhicules et confection d'horaires

Thèse réalisée en cotutelle entre l'Université de Montréal et l'Université de Technologie de Troyes

L’utilisation de la polarimétrie radar et de la décomposition de Touzi pour la caractérisation et la classification des physionomies végétales des milieux humides : le cas du Lac Saint-Pierre.

Les milieux humides remplissent plusieurs fonctions écologiques d’importance et contribuent à la biodiversité de la faune et de la flore. Même s’il existe une reconnaissance croissante sur l’importante de protéger ces milieux, il n’en demeure pas moins que leur intégrité est encore menacée par la pression des activités humaines. L’inventaire et le suivi systématique des milieux humides constituent une nécessité et la télédétection est le seul moyen réaliste d’atteindre ce but. L’objectif de cette thèse consiste à contribuer et à améliorer la caractérisation des milieux humides en utilisant des données satellites acquises par des radars polarimétriques en bande L (ALOS-PALSAR) et C (RADARSAT-2). Cette thèse se fonde sur deux hypothèses (chap. 1). La première hypothèse stipule que les classes de physionomies végétales, basées sur la structure des végétaux, sont plus appropriées que les classes d’espèces végétales car mieux adaptées au contenu informationnel des images radar polarimétriques. La seconde hypothèse stipule que les algorithmes de décompositions polarimétriques permettent une extraction optimale de l’information polarimétrique comparativement à une approche multipolarisée basée sur les canaux de polarisation HH, HV et VV (chap. 3). En particulier, l’apport de la décomposition incohérente de Touzi pour l’inventaire et le suivi de milieux humides est examiné en détail. Cette décomposition permet de caractériser le type de diffusion, la phase, l’orientation, la symétrie, le degré de polarisation et la puissance rétrodiffusée d’une cible à l’aide d’une série de paramètres extraits d’une analyse des vecteurs et des valeurs propres de la matrice de cohérence. La région du lac Saint-Pierre a été sélectionnée comme site d’étude étant donné la grande diversité de ses milieux humides qui y couvrent plus de 20 000 ha. L’un des défis posés par cette thèse consiste au fait qu’il n’existe pas de système standard énumérant l’ensemble possible des classes physionomiques ni d’indications précises quant à leurs caractéristiques et dimensions. Une grande attention a donc été portée à la création de ces classes par recoupement de sources de données diverses et plus de 50 espèces végétales ont été regroupées en 9 classes physionomiques (chap. 7, 8 et 9). Plusieurs analyses sont proposées pour valider les hypothèses de cette thèse (chap. 9). Des analyses de sensibilité par diffusiogramme sont utilisées pour étudier les caractéristiques et la dispersion des physionomies végétales dans différents espaces constitués de paramètres polarimétriques ou canaux de polarisation (chap. 10 et 12). Des séries temporelles d’images RADARSAT-2 sont utilisées pour approfondir la compréhension de l’évolution saisonnière des physionomies végétales (chap. 12). L’algorithme de la divergence transformée est utilisé pour quantifier la séparabilité entre les classes physionomiques et pour identifier le ou les paramètres ayant le plus contribué(s) à leur séparabilité (chap. 11 et 13). Des classifications sont aussi proposées et les résultats comparés à une carte existante des milieux humide du lac Saint-Pierre (14). Finalement, une analyse du potentiel des paramètres polarimétrique en bande C et L est proposé pour le suivi de l’hydrologie des tourbières (chap. 15 et 16). Les analyses de sensibilité montrent que les paramètres de la 1re composante, relatifs à la portion dominante (polarisée) du signal, sont suffisants pour une caractérisation générale des physionomies végétales. Les paramètres des 2e et 3e composantes sont cependant nécessaires pour obtenir de meilleures séparabilités entre les classes (chap. 11 et 13) et une meilleure discrimination entre milieux humides et milieux secs (chap. 14). Cette thèse montre qu’il est préférable de considérer individuellement les paramètres des 1re, 2e et 3e composantes plutôt que leur somme pondérée par leurs valeurs propres respectives (chap. 10 et 12). Cette thèse examine également la complémentarité entre les paramètres de structure et ceux relatifs à la puissance rétrodiffusée, souvent ignorée et normalisée par la plupart des décompositions polarimétriques. La dimension temporelle (saisonnière) est essentielle pour la caractérisation et la classification des physionomies végétales (chap. 12, 13 et 14). Des images acquises au printemps (avril et mai) sont nécessaires pour discriminer les milieux secs des milieux humides alors que des images acquises en été (juillet et août) sont nécessaires pour raffiner la classification des physionomies végétales. Un arbre hiérarchique de classification développé dans cette thèse constitue une synthèse des connaissances acquises (chap. 14). À l’aide d’un nombre relativement réduit de paramètres polarimétriques et de règles de décisions simples, il est possible d’identifier, entre autres, trois classes de bas marais et de discriminer avec succès les hauts marais herbacés des autres classes physionomiques sans avoir recours à des sources de données auxiliaires. Les résultats obtenus sont comparables à ceux provenant d’une classification supervisée utilisant deux images Landsat-5 avec une exactitude globale de 77.3% et 79.0% respectivement. Diverses classifications utilisant la machine à vecteurs de support (SVM) permettent de reproduire les résultats obtenus avec l’arbre hiérarchique de classification. L’exploitation d’une plus forte dimensionalitée par le SVM, avec une précision globale maximale de 79.1%, ne permet cependant pas d’obtenir des résultats significativement meilleurs. Finalement, la phase de la décomposition de Touzi apparaît être le seul paramètre (en bande L) sensible aux variations du niveau d’eau sous la surface des tourbières ouvertes (chap. 16). Ce paramètre offre donc un grand potentiel pour le suivi de l’hydrologie des tourbières comparativement à la différence de phase entre les canaux HH et VV. Cette thèse démontre que les paramètres de la décomposition de Touzi permettent une meilleure caractérisation, de meilleures séparabilités et de meilleures classifications des physionomies végétales des milieux humides que les canaux de polarisation HH, HV et VV. Le regroupement des espèces végétales en classes physionomiques est un concept valable. Mais certaines espèces végétales partageant une physionomie similaire, mais occupant un milieu différent (haut vs bas marais), ont cependant présenté des différences significatives quant aux propriétés de leur rétrodiffusion.