Inherently chiral calix[4]arenes with planar chirality: two new entries to the family

The synthesis of two new inherently chiral calix[4]arenes (ICCs, 1 and 2), endowed with electron-rich concave surfaces, has been achieved through the desymmetrization of a lower rim distal-bridged oxacyclophane (OCP) macrocycle. The new highly emissive ICCs were resolved by chiral HPLC, and the enantiomeric nature of the isolated antipodes proved by electronic circular dichroism (CD). Using time-dependent density functional calculations of CD spectra, their absolute configurations were established. NMR studies with (S)-Pirkle's alcohol unequivocally showed that the host-guest interactions occur in the chiral pocket comprehending the calix-OCP exo cavities and the carbazole moieties.

Fractional analysis of traffic dynamics

This article presents a dynamical analysis of several traffic phenomena, applying a new modelling formalism based on the embedding of statistics and Laplace transform. The new dynamic description integrates the concepts of fractional calculus leading to a more natural treatment of the continuum of the Transfer Function parameters intrinsic in this system. The results using system theory tools point out that it is possible to study traffic systems, taking advantage of the knowledge gathered with automatic control algorithms. Dynamics, Games and Science I Dynamics, Games and Science I Look Inside Other actions Export citation About this Book Reprints and Permissions Add to Papers Share Share this content on Facebook Share this content on Twitter Share this content on LinkedIn

Synthesis of Sub-5 NM Co-Doped SnO2 nanoparticles and their structural microstructural, optical and photocatalytic properties

A swift chemical route to synthesize Co-doped SnO2 nanopowders is described. Pure and highly stable Sn1-xCoxO2-delta (0 <= x <= 0.15) crystalline nanoparticles were synthesized, with mean grain sizes <5 nm and the dopant element homogeneously distributed in the SnO2 matrix. The UV-visible diffuse reflectance spectra of the Sn1-xCoxO2-delta samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The samples' Urbach energies were calculated and correlated with their bandgap energies. The photocatalytic activity of the Sn1-xCoxO2-delta samples was investigated for the 4-hydroxylbenzoic acid (4-HBA) degradation process. A complete photodegradation of a 10 ppm 4-HBA solution was achieved using 0.02% (w/w) of Sn0.95Co0.05O2-delta nanoparticles in 60 min of irradiation. (C) 2014 Elsevier B.V. All rights reserved.

The 1998 Faial earthquake, Azores: Evidence for a transform fault associated with the Nubia-Eurasia plate boundary?

With very few exceptions, M > 4 tectonic earthquakes in the Azores show normal fault solution and occur away from the islands. Exceptionally, the 1998 shock was pure strike-slip and occurred within the northern edge of the Pico-Faial Ridge. Fault plane solutions show two possible planes of rupture striking ENE-WSW (dextral) and NNW-SSE (sinistral). The former has not been recognised in the Azores, but is parallel to the transform direction related to the relative motion between the Eurasia and Nubia plates. Therefore, the main question we address in the present study is: do transform faults related to the Eurasia/Nubia plate boundary exist in the Azores? Knowing that the main source of strain is related to plate kinematics, we conclude that the sinistral strike-slip NNW-SSE fault plane solution is not consistent with either the fault dip (ca. 65, which is typical of a normal fault) or the ca. ENE-WSW direction of maximum extension; both are consistent with a normal fault, as observed in most major earthquakes on faults striking around NNW-SSE in the Azores. In contrast, the dextral strike-slip ENE-WSW fault plane solution is consistent with the transform direction related to the anticlockwise rotation of Nubia relative to Eurasia. Altogether, tectonic data, measured ground motion, observed destruction, and modelling are consistent with a dextral strike-slip source fault striking ENE-WSW. Furthermore, the bulk clockwise rotation measured by GPS is typical of bookshelf block rotations observed at the termination of such master strike-slip faults. Therefore, we suggest that the 1998 earthquake can be related to the WSW termination of a transform (ENE-WSW fault plane solution) associated with the Nubia-Eurasia diffuse plate boundary. (C) 2014 Elsevier B.V. All rights reserved.

Human-robot teamwork: a knowledge-based solution

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Electrotécnica e de Computadores

Substituted P-Phenylene Ethynylene trimers as fluorescent sensors for nitroaromatic explosives

New sensory materials based on p-phenylene ethynylene trimers integrating calix[4]arene receptors (CALIX-PET) and tert-butylphenol (TBP-PET) moieties have been synthesized and their sensitivity and selectivity for the detection of nitroaromatic compounds (NACs) such as nitrobenzene (NB), 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and picric acid (PA) investigated in fluid phase and solid-state. It was found that both fluorophores displayed high sensitivities toward NACs detection in solution as evaluated by the Stern-Volmer formalism. For all the tested explosives, the ratio of fluorescence intensities (F-0/F) is a linear function of the quencher concentration only after appropriate correction of fluorescence quenching data for inner-filter effects. The quenching efficiencies for CALIX-PET and TBP-PET follow the order PA >> TNT > DNT > NB, which correlate well with the quenchers electron affinities as evaluated from their LUMOs energies thereby suggesting a photoinduced electron transfer as the dominant mechanism of fluorescence quenching. The selectivity of these sensors was checked against exemplar interferents possessing differentiated electronic properties (benzoic acid, 2,4-dichlorophenol and benzoquinone) and reduced quenching activity was detected. The quenching efficiencies and response times of the two fluorophores in the solid-state toward NB, 2,4-DNT and TNT vapors were evaluated through steady-state fluorescence quenching experiments with the materials dispersed in polymeric matrices or as neat films. The most significant fluorescence quenching responses were achieved for drop-casted films of TBP-PET upon exposure to nitroaromatics.

Simulation and dynamics of freeway traffic

This paper presents the new package entitled Simulator of Intelligent Transportation Systems (SITS) and a computational oriented analysis of traffic dynamics. The SITS adopts a microscopic simulation approach to reproduce real traffic conditions considering different types of vehicles, drivers and roads. A set of experiments with the SITS reveal the dynamic phenomena exhibited by this kind of system. For this purpose a modelling formalism is developed that embeds the statistics and the Laplace transform. The results make possible the adoption of classical system theory tools and point out that it is possible to study traffic systems taking advantage of the knowledge gathered with automatic control algorithms. A complementary perspective for the analysis of the traffic flow is also quantified through the entropy measure.

Fractional order electromagnetics

The Maxwell equations constitute a formalism for the development of models describing electromagnetic phenomena. The four Maxwell laws have been adopted successfully in many applications and involve only the integer order differential calculus. Recently, a closer look for the cases of transmission lines, electrical motors and transformers, that reveal the so-called skin effect, motivated a new perspective towards the replacement of classical models by fractional-order mathematical descriptions. Bearing these facts in mind this paper addresses the concept of static fractional electric potential. The fractional potential was suggested some years ago. However, the idea was not fully explored and practical methods of implementation were not proposed. In this line of thought, this paper develops a new approximation algorithm for establishing the fractional order electrical potential and analyzes its characteristics.

Desenvolvimento de ferramentas e provetes para o ensaio Thick Adherend Shear Test (TAST).

As estruturas coladas são geralmente projetadas para que o adesivo seja essencialmente sujeito a esforços de corte, pois neste tipo de solicitação o adesivo apresenta melhores caraterísticas mecânicas. A avaliação do comportamento ao corte pode ser realizada com o adesivo no estado maciço ou como camada fina em juntas adesivas. Os métodos que permitem avaliar o comportamento ao corte, quer para o adesivo, quer para as juntas, são: o ensaio Iosipescu ou V-Notched beam shear method, o ensaio de borboleta ou Notched plate shear method (Arcan), o ensaio de torsão, o ensaio de tração numa junta de sobreposição simples e o ensaio Thick Adherend Shear Test (TAST). Os ensaios Arcan e Iosipescu, tal como o ensaio de torção, podem ser realizados em provetes de adesivo maciço ou em juntas. O ensaio de torção é pouco utilizado, porque a aplicação do esforço de corte exige dispositivos e equipamentos de ensaios complexos. Os ensaios Arcan e Iosipescu utilizam provetes com entalhes e podem introduzir alguma dificuldade na medição precisa das deformações. O ensaio de tração numa junta de sobreposição simples é um dos métodos mais usados para caraterizar uma junta adesiva, porque é um método simples, as juntas são de fácil fabrico e pode ser realizado em máquinas universais de ensaios mecânicos. Neste ensaio os aderentes estão sujeitos a uma solicitação de tração, enquanto a camada de adesivo está sujeita a esforços de corte combinados com esforços de arrancamento. Os esforços de arrancamento resultam da própria geometria da junta na qual existe um desalinhamento das forças de tração, mesmo quando são colocados calços (reguladores de espessura) nos locais de amarração. O ensaio TAST é dos mais populares para obtenção das propriedades ao corte, uma vez que tanto as ferramentas de ensaio como o fabrico dos provetes são relativamente simples. Este ensaio é realizado em junta sendo os substratos espessos e de aço que, devido à sua elevada rigidez, contribuem para um esforço de corte praticamente puro no adesivo. Neste trabalho realizou-se o projeto e a fabricação das ferramentas, gabarit e substratos necessários para a execução de provetes TAST e ensaios utilizando diferentes adesivos.

Membrane design and characterisation by incorporation of ionic liquids

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química, especialidade de Operações Unitárias e Fenómenos de Transferência, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Retratos de um Bairro : a fotografia como forma de comunicação

Trabalho de projeto apresentado à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Audiovisual e Multimédia.

Comparative studies of Yersinia pestis outer membrane isolation techniques and their potential use in plague epidemiology

In the present study three techniques for obtaining outer membrane enriched fractions from Yersinia pestis were evaluated. The techniques analysed were: differential solubilization of the cytoplasmic membrane with Sarkosyl or Triton X-100, and centrifugation in sucrose density gradients. The sodium dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) of outer membrane isolated by the different methods resulted in similar protein patterns. The measurement of NADH-dehydrogenase and succinate dehydrogenase (inner membrane enzymes) indicated that the outer membrane preparations obtained by the three methods were pure enough for analytical studies. In addition, preliminary evidences on the potential use of outer membrane proteins for the identification of geographic variants of Y. pestis wild isolates are presented.

Probabilistic tsunami hazard in the Northeast Atlantic from near- and far-field tectonic sources

In this article, we present the first study on probabilistic tsunami hazard assessment for the Northeast (NE) Atlantic region related to earthquake sources. The methodology combines the probabilistic seismic hazard assessment, tsunami numerical modeling, and statistical approaches. We consider three main tsunamigenic areas, namely the Southwest Iberian Margin, the Gloria, and the Caribbean. For each tsunamigenic zone, we derive the annual recurrence rate for each magnitude range, from Mw 8.0 up to Mw 9.0, with a regular interval, using the Bayesian method, which incorporates seismic information from historical and instrumental catalogs. A numerical code, solving the shallow water equations, is employed to simulate the tsunami propagation and compute near shore wave heights. The probability of exceeding a specific tsunami hazard level during a given time period is calculated using the Poisson distribution. The results are presented in terms of the probability of exceedance of a given tsunami amplitude for 100- and 500-year return periods. The hazard level varies along the NE Atlantic coast, being maximum along the northern segment of the Morocco Atlantic coast, the southern Portuguese coast, and the Spanish coast of the Gulf of Cadiz. We find that the probability that a maximum wave height exceeds 1 m somewhere in the NE Atlantic region reaches 60 and 100 % for 100- and 500-year return periods, respectively. These probability values decrease, respectively, to about 15 and 50 % when considering the exceedance threshold of 5 m for the same return periods of 100 and 500 years.

Anatase as an alternative application for preventing biodeterioration of mortars: evaluation and comparison with other biocides

International Biodeterioration & Biodegradation 64(2010)388 e 396

Zonal distribution of gold and platinium group elements in the Mondunguara deposits Mozambique

The Mondunguara copper mines are situated in mountainous terrain in west-central Mozambique. The mineralization consists of chalcopyrite, pyrrhotite, common pcntlandite, cobaltpentlandite, pyrite and several minor oxides and sulphides in tabular ore bodies deeping steep to the north. Gold was known to occur in small quantities but no systematic sampling and analysis for precious clements was ever done. Mineralogical and geological evidence has shown that the ores are magmatic in origin and were derived from gabbro-peridotitic magma dykes saturated in sulphides when intruded. The ore bodies show a clear zonation. Platinum group elements as well as pure gold are associated with high temperature hexagonal pyrrhotite. This pyrrhotite being of no use is generally discarded to the tailing dumps. Late hydrothermal phases are enriched in native silver, silver tellurides as well as electrum.