Automated Identification and Classification of Stereochemistry: Chirality and Double Bond Stereoisomerism

Stereoisomers have the same molecular formula and the same atom connectivity and their existence can be related to the presence of different three-dimensional arrangements. Stereoisomerism is of great importance in many different fields since the molecular properties and biological effects of the stereoisomers are often significantly different. Most drugs for example, are often composed of a single stereoisomer of a compound, and while one of them may have therapeutic effects on the body, another may be toxic. A challenging task is the automatic detection of stereoisomers using line input specifications such as SMILES or InChI since it requires information about group theory (to distinguish stereoisomers using mathematical information about its symmetry), topology and geometry of the molecule. There are several software packages that include modules to handle stereochemistry, especially the ones to name a chemical structure and/or view, edit and generate chemical structure diagrams. However, there is a lack of software capable of automatically analyzing a molecule represented as a graph and generate a classification of the type of isomerism present in a given atom or bond. Considering the importance of stereoisomerism when comparing chemical structures, this report describes a computer program for analyzing and processing steric information contained in a chemical structure represented as a molecular graph and providing as output a binary classification of the isomer type based on the recommended conventions. Due to the complexity of the underlying issue, specification of stereochemical information is currently limited to explicit stereochemistry and to the two most common types of stereochemistry caused by asymmetry around carbon atoms: chiral atom and double bond. A Webtool to automatically identify and classify stereochemistry is available at http://nams.lasige.di.fc.ul.pt/tools.ph

Linear Invariant Systems Theory for Signal Enhancement

This paper discusses a linear time invariant (LTI) systems approach to signal enhancement via projective subspace techniques. It provides closed form expressions for the frequency response of data adaptive finite impulse response eigenfilters. An illustrative example using speech enhancement is also presented.Este artigo apresenta a aplicação da teoria de sistemas lineares invariantes no tempo (LTI) na análise de técnicas de sub-espaço. A resposta em frequência dos filtros resultantes da decomposição em valores singulares é obtida aplicando as propriedades dos sistemas LTI

Nonequilibrium stationary states of 3D self-gravitating systems

Three dimensional self-gravitating systems do not evolve to thermodynamic equilibrium, but become trapped in nonequilibrium quasistationary states. In this Letter we present a theory which allows us to a priori predict the particle distribution in a final quasistationary state to which a self-gravitating system will evolve from an initial condition which is isotropic in particle velocities and satisfies a virial constraint 2K=-U, where K is the total kinetic energy and U is the potential energy of the system

SSA of biomedical signals: A linear invariant systems approach

Singular spectrum analysis (SSA) is considered from a linear invariant systems perspective. In this terminology, the extracted components are considered as outputs of a linear invariant system which corresponds to finite impulse response (FIR) filters. The number of filters is determined by the embedding dimension.We propose to explicitly define the frequency response of each filter responsible for the selection of informative components. We also introduce a subspace distance measure for clustering subspace models. We illustrate the methodology by analyzing lectroencephalograms (EEG).FCT - PhD scholarship (SFRH/BD/28404/2006)FCT - PhD scholarship (SFRH/BD/48775/2008

À descoberta de sofware para explorar a programação linear no ensino secundário

A Programação Linear, PL, tem como objectivo a resolução de problemas de optimização com restrições em que todas as funções envolvidas são lineares. Diversos problemas da vida real podem ser formulados como problemas de PL como, por exemplo, os problemas de planeamento e de transportes. A Programação Linear é um dos temas obrigatórios de algumas disciplinas de Matemática do Ensino Secundário, sendo importante que se trabalhem com os alunos problemas que traduzam situações reais, ou suas adaptações. Como estes problemas nem sempre são fáceis e rápidos de resolver, a utilização de ferramentas tecnológicas na sua resolução reveste-se de enorme importância. Existem diversos programas de computador como o Solver do Microsoft Office Excel, o WinQSB, o Programación Lineal e o Winplot, de fácil utilização pelos alunos, que possibilitam a exploração gráfica, no caso bidimensional, ou analítica dos problemas de PL. O uso deste software permite que os alunos resolvam uma maior diversidade de problemas e se centrem mais na análise e interpretação de resultados. Neste artigo, ilustra-se, resumidamente, a forma de resolver problemas de PL com o software mencionado e discute-se as suas potencialidades e limitações

Linear programming knowledge in first stage higher education courses

In this work we will describe an experimental study with approximately fifty Portuguese students of the 2nd year of the BSc Degree of Biomedical Engineering as well as Chemical and Biological Engineering Higher Education Courses. The aims of this study are to identify which knowledge of Linear Programming (LP) taught in High School the students acquired and still remember, which tools they used in that stage of education when learning the theme of LP and their opinion about the significance of LP in daily life problem resolution. We also propose to investigate if the students are able to use WinQSB software to solve LP problems. In addition, we intend to identify not only the versatility of this software but also the opinion of the students about the resolution of LP problems with WinQSB, as well as their main difficulties during this experience

A Comprehensive Metabolic Profile of Cultured Astrocytes Using Isotopic Transient Metabolic Flux Analysis and 13C-Labeled Glucose

Metabolic models have been used to elucidate important aspects of brain metabolism in recent years. This work applies for the first time the concept of isotopic transient 13C metabolic flux analysis (MFA) to estimate intracellular fluxes in primary cultures of astrocytes. This methodology comprehensively explores the information provided by 13C labeling time-courses of intracellular metabolites after administration of a 13C-labeled substrate. Cells were incubated with medium containing [1-13C]glucose for 24 h and samples of cell supernatant and extracts collected at different time points were then analyzed by mass spectrometry and/or high performance liquid chromatography. Metabolic fluxes were estimated by fitting a carbon labeling network model to isotopomer profiles experimentally determined. Both the fast isotopic equilibrium of glycolytic metabolite pools and the slow labeling dynamics of TCA cycle intermediates are described well by the model. The large pools of glutamate and aspartate which are linked to the TCA cycle via reversible aminotransferase reactions are likely to be responsible for the observed delay in equilibration of TCA cycle intermediates. Furthermore, it was estimated that 11% of the glucose taken up by astrocytes was diverted to the pentose phosphate pathway. In addition, considerable fluxes through pyruvate carboxylase [PC; PC/pyruvate dehydrogenase (PDH) ratio = 0.5], malic enzyme (5% of the total pyruvate production), and catabolism of branched-chained amino acids (contributing with ∼40% to total acetyl-CoA produced) confirmed the significance of these pathways to astrocytic metabolism. Consistent with the need of maintaining cytosolic redox potential, the fluxes through the malate–aspartate shuttle and the PDH pathway were comparable. Finally, the estimated glutamate/α-ketoglutarate exchange rate (∼0.7 μmol mg prot−1 h−1) was similar to the TCA cycle flux. In conclusion, this work demonstrates the potential of isotopic transient MFA for a comprehensive analysis of energy metabolism

Chemical composition and anti-diabetic properties of Cytisus multiflorus

Bakground and aims: The interest on plants with potential medicinal properties has been increasing worldwide. In the Iberian Peninsula there are some endemic species known by the population for their pharmacologic activity with valorization potential that have not been yet characterized. The white Spanish broom (Cytisus multiflorus) is described as having anti-diabetic effect [1] and in a preliminary the hypoglycemic and hyper-insulinemic effect of an aqueous extract has been shown [2]. The aim of this work was to fractionate and analyse the composition of the aqueous extract of C. multiflorus flowering parts and evaluate its potential as an anti-diabetic agent. Materials and methods: The aqueous extract was primarily fractionated by SPE using water:methanol (W:Me) eluent (a 10% step-wise gradient W:Me from 100:0 to 0:100) followed by high performance liquid chromatography with diode array detector (HPLC-DAD). The most relevant fraction were analysed by LC-MS to determine the chemical composition. Total fenol content was determined by a modified Folin-Ciocalteau method and the anti-oxidant activity was evaluated by the DPPH mehod. Finally, the hipoglicemic potential was evaluated in vivo using glucose intolerant rats (GIR). Results: Eleven fractions of the bulk extract were obtained. Seven of these fractions (10, 30, 40, 50, 60, 70 e 80% Me) were found to have a relevant compounds, mostly flavonoid compounds, namely, rutin (50, 60 and 70% Me fractions), ferrulic acid (30% Me), referred as having hypoglicemic effect. The fractions obtained with 50 and 70% Me showed the highest content in phenol equivalents and the highest anti-oxidant effect were found in the 50 and 60% Me fractions. The 30 and 60% Me fraction had no effect on the post-prandial glicemia. Conclusions: The 30, 50, 60 and 70% Me fractions, due to their chemical composition and anti-oxidant effects were the most promising to have anti-diabetic effect. However, the 30 and 60% Me were found to be ineffective. The 50% Me fraction showed both a high content of flavonoid compounds and the highest anti-oxidant power which suggest that it may constitute the most promising one. The anti-diabetic properties of this fraction should be investigated. [1] Camejo-Rodrigues J. et al. (2003). J. Ethnopharmacol, 89, 199-209 [2] Célia M. Antunes, Laurinda R. Areias, Inês P. Vieira, Ana C. Costa, M. Teresa Tinoco, & Júlio Cruz-Morais (2009). Rev. Fitoterapia 9 (Supl.1): 91

Proton conductivity of Nafion-azolebisphosphonates membranes for PEM fuel cells

Energy systems with cleaner and sustainable sources are crucial challenges of the 21st century to deal with the environmental threat of global warming and the declining reserves of fossil fuels. Fuel cells are electrochemical devices that convert the chemical energy stored in a fuel directly into electrical energy, providing electrical energy with high efficiency and low environmental impact. Among them, proton exchange membrane fuel cells (PEMFCs) are considered promising power sources, due to their high power density and high power-to-weight ratio but their performance depends crucially on their proton exchange membranes [1]. Usually, these membranes are made of organic polymers containing acidic functionalities (ex. Nafion® ), which proton transport properties strongly depend on their water content and, consequently, limit their operation temperatures up to 90ºC. Preliminary studies have demonstrated that incorporation of aryl-bisphosphonic acids into Nafion, by casting, results in an enhancement of the proton conductivity of the membrane. The aim of this work was the preparation of new Nafion membranes doped with azolebisphosphonates derivatives, which could act as a source of protons and also function as proton acceptors, facilitating the intermolecular transmission of protons through the membrane

Intervenciones para depresión en jóvenes: de la reducción de síntomas al bienestar y funcionamiento óptimo

Depression is a major public health problem in children and adolescents, which makes the identification and implementation of effective interventions an increasing concern. Therefore, the main aim of this article is to discuss theoretically different psychological interventions for depression. In particular, those focused on psychopathology and depressive symptom reduction and the new interventions based on the positive psychology approach, which focus on optimal functioning and wellbeing. Empirically supported interventions for children and adolescents, such as cognitive-behavioral therapy (CBT) and interpersonal therapy (IPT), have focus on symptom reduction, which represents an incomplete vision of youth functioning. In contrast, interventions based on positive psychology promote a more balanced approach that takes into consideration the negative and positive aspects of experience and aims to enhance well-being. We present and discuss new interventions, such as the Optimal Functioning Therapy for Adolescents, which suggest that the focus of interventions for depressed adolescents should integrate symptom reduction and well-being enhancement to achieve optimal functioning. Helping young people be happier and more engaged in their lives is part of a new perspective for clinical psychology practice.La depresión es un problema de salud pública importante en niños y adolescentes, lo que hace que identificar e implementar intervenciones efectivas para su tratamiento sea de creciente interés. Por lo tanto, el objetivo principal de este artículo es discutir teóricamente diferentes intervenciones psicológicas para la depresión. En particular, las que se abordan la psicopatología, la reducción de los síntomas depresivos y las nuevas intervenciones basadas en el enfoque de la psicología positiva, que se centran en el funcionamiento óptimo y el bienestar de la persona. Intervenciones con respaldo empírico para los niños y adolescentes, como la terapia cognitivo-conductual (TCC) y la terapia interpersonal (IPT), tienen un enfoque de reducción de síntomas, lo que representa una visión incompleta de funcionamiento en la juventud. En contraste, las intervenciones basadas en la psicología positiva promueven una aproximación más equilibrada que contempla los aspectos negativos y positivos de la experiencia y tiene como objetivo mejorar el bienestar. En el artículo, se presentan y discuten intervenciones nuevas, como la Terapia del Funcionamiento Óptimo Terapia para Adolescentes, que sugieren que el enfoque de las intervenciones para los adolescentes con depresión debería integrar la reducción de síntomas y la mejora de su bienestar para lograr un funcionamiento óptimo. Ayudar a que los jóvenes sean más felices y más comprometidos en sus vidas es parte de una nueva perspectiva para la práctica de la psicología clínica.info:eu-repo/semantics/publishedVersio