Density functional theory study of the interaction between CO and on a Pt surface:CO/Pt(111), O/Pt(111), and CO/O/Pt(111)

Ab initio total energy calculations within the Density Functional Theory framework were carried out for Pt(111), Pt(111)-p(2x2)-CO, Pt(111)-p(2x2)-O, and Pt(111)-p(2x2)-(CO+O) to provide an insight into the interaction between CO and O on metal surfaces, an important issue in CO oxidation, and also in promotion and poisoning effects of catalysis. The geometrical structures of these systems were optimized with respect to the total energy, the results of which agree with existing experimental values very well. It is found that (i) the local structures of Pt(111)-p(2x2)-(CO+O), such as the bond lengths of C-O, C-Pt, and O-Pt (chemisorbed O atom with Pt), are almost the same as that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively, (ii) the total valence charge density distributions in Pt(111)-p(2x2)-(CO+O) are very similar to that in Pt(111)-p(2x2)-CO, except in the region of the chemisorbed oxygen atom, and also nearly identical to that in Pt(111)-p(2x2)-O, apart from in the region of the chemisorbed CO, and (iii) the chemisorption energy of CO on a precovered Pt(111)-p(2x2)-O and the chemisorption energy of O on a precovered Pt(111)-p(2x2)CO are almost equal to that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively. These results indicate that the interaction between CO and chemisorbed oxygen on a metal surface is mainly shore range in nature. The discussions of Pt-CO and Pt-O bonding and the interaction between CO and the chemisorbed oxygen atom on Pt(111) are augmented by local densities of states and real space distributions of quantum states.

A density functional theory study on the interaction between chemisorbed CO and S on Rh(111)

Density functional theory calculations are carried out for Rh(111)-p(2 x 2)-CO, Rh(111)-p(2 x 2)-S, Rh(111)-p(2 x 2)-(S + CO), Rh(111)-p(3 x 3)-CO, Rh(111)-p(3 x 3)-S and Rh(111)-p(3 x 3)-(S + CO), aiming to shed some light on the S poisoning effect. Geometrical structures of these systems are optimized and chemisorption energies are determined. The presence of S does not significantly influence the geometrical structure and chemisorption energy of CO and vice versa, which strongly suggests that the interaction between CO and S on the Rh(111) surface is mainly short-range in nature. The long range electronic effect for the dramatic attenuation of the CO methanation activity by sulfur is likely to be incorrect. It is suggested that an ensemble effect may be dominant in the catalytic deactivation. (C) 1999 Elsevier Science B.V. All rights reserved.

Properties of extragalactic dust inferred from linear polarimetry of Type Ia Supernovae

Aims
The aim of this paper is twofold: 1) to investigate the properties of extragalactic dust and compare them to what is seen in the Galaxy; 2) to address in an independent way the problem of the anomalous extinction curves reported for reddened Type Ia Supernovae (SN) in connection to the environments in which they explode. 

Methods
The properties of the dust are derived from the wavelength dependence of the continuum polarization observed in four reddened Type Ia SN: 1986G, 2006X, 2008fp, and 2014J. The method is based on the observed fact that Type Ia SN have a negligible intrinsic continuum polarization. This and their large luminosity makes them ideal tools to probe the dust properties in extragalactic environments.

Results
All four objects are characterized by exceptionally low total-to-selective absorption ratios (R<inf>V</inf>) and display an anomalous interstellar polarization law, characterized by very blue polarization peaks. In all cases the polarization position angle is well aligned with the local spiral structure. While SN 1986G is compatible with the most extreme cases of interstellar polarization known in the Galaxy, SN 2006X, 2008fp, and 2014J show unprecedented behaviours. The observed deviations do not appear to be connected to selection effects related to the relatively large amounts of reddening characterizing the objects in the sample.

Conclusions
The dust responsible for the polarization of these four SN is most likely of interstellar nature. The polarization properties can be interpreted in terms of a significantly enhanced abundance of small grains. The anomalous behaviour is apparently associated with the properties of the galactic environment in which the SN explode, rather than with the progenitor system from which they originate. For the extreme case of SN 2014J, we cannot exclude the contribution of light scattered by local material; however, the observed polarization properties require an ad hoc geometrical dust distribution.

Mer and fac isomerism in tris chelate diimine metal complexes

In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity. 

Nonreciprocal nonlinear scattering by stacked magnetoactive semiconductor layers

The combinatorial frequency generation by the periodic stacks of magnetically biased semiconductor layers has been modelled in the self-consistent problem formulation, taking into account the nonlinear dynamics of carriers. It has been shown that the nonlinear response of the magnetoactive semiconductor periodic structure is strongly enhanced by magnetic bias and combinations of the layer physical and geometrical parameters. The effects of the pump wave nonreciprocal reflectance and field displacement on the efficiency of three-wave mixing process is illustrated by the simulation results

Investigation of the temperature homogeneity of die melt flows in polymer extrusion

Polymer extrusion is fundamental to the processing of polymeric materials and melt flow temperature homogeneity is a major factor which influences product quality. Undesirable thermal conditions can cause problems such as melt degradation, dimensional instability, weaknesses in mechanical/optical/geometrical properties, and so forth. It has been revealed that melt temperature varies with time and with radial position across the die. However, the majority of polymer processes use only single-point techniques whose thermal measurements are limited to the single point at which they are fixed. Therefore, it is impossible for such techniques to determine thermal homogeneity across the melt flow. In this work, an extensive investigation was carried out into melt flow thermal behavior of the output of a single extruder with different polymers and screw geometries over a wide range of processing conditions. Melt temperature profiles of the process output were observed using a thermocouple mesh placed in the flow and results confirmed that the melt flow thermal behavior is different at different radial positions. The uniformity of temperature across the melt flow deteriorated considerably with increase in screw rotational speed while it was also shown to be dependent on process settings, screw geometry, and material properties. Moreover, it appears that the effects of the material, machine, and process settings on the quantity and quality of the process output are heavily coupled with each other and this may cause the process to be difficult to predict and variable in nature

A technique for reducing strain concentrations in FRP wrapped concrete columns

Existing studies have shown conclusively that the measured fibre reinforced polymer (FRP) rupture strain in FRP wrapped concrete columns is usually significantly smaller than the rupture strain obtained from flat coupon tests. One of the main causes for this phenomenon is the existence of geometrical discontinuities at both ends of the FRP sheets. This study proposes a new strengthening method in which continuous FRP spiral wrapping is used to eliminate strain concentrations due to the geometrical discontinuities and thus increase the FRP rupture strain at column failure. The effect of the spiral angle of FRP on the FRP rupture strain in FRP wrapped specimens was experimentally investigated. The test results indicate that the spiral wrapping with a small angle with respect to the column circumference can significantly increase the strain efficiency of FRP and thus enhance the axial compression capacity of the strengthened cylinders.

The vascular targeting agent combretastatin-A4 and a novel cis-Restricted {beta}-Lactam Analogue, CA-432, induce apoptosis in human chronic myeloid leukemia cells and ex vivo patient samples including those displaying multidrug resistance

Combretastatin-A4 (CA-4) is a natural derivative of the African willow tree Combretum caffrum. CA-4 is one of the most potent antimitotic components of natural origin, but it is, however, intrinsically unstable. A novel series of CA-4 analogs incorporating a 3,4-diaryl-2-azetidinone (β-lactam) ring were designed and synthesized with the objective to prevent cis -trans isomerization and improve the intrinsic stability without altering the biological activity of CA-4. Evaluation of selected β-lactam CA-4 analogs demonstrated potent antitubulin, antiproliferative, and antimitotic effects in human leukemia cells. A lead β-lactam analog, CA-432, displayed comparable antiproliferative activities with CA-4. CA-432 induced rapid apoptosis in HL-60 acute myeloid leukemia cells, which was accompanied by depolymerization of the microtubular network, poly(ADP-ribose) polymerase cleavage, caspase-3 activation, and Bcl-2 cleavage. A prolonged G(2)M cell cycle arrest accompanied by a sustained phosphorylation of mitotic spindle checkpoint protein, BubR1, and the antiapoptotic proteins Bcl-2 and Bcl-x(L) preceded apoptotic events in K562 chronic myeloid leukemia (CML) cells. Molecular docking studies in conjunction with comprehensive cell line data rule out CA-4 and β-lactam derivatives as P-glycoprotein substrates. Furthermore, both CA-4 and CA-432 induced significantly more apoptosis compared with imatinib mesylate in ex vivo samples from patients with CML, including those positive for the T315I mutation displaying resistance to imatinib mesylate and dasatinib. In summary, synthetic intrinsically stable analogs of CA-4 that display significant clinical potential as antileukemic agents have been designed and synthesized.

Thiol isomerases negatively regulate the cellular shedding activity of ADAM17

ADAM17 (where ADAM is 'a disintegrin and metalloproteinase') can rapidly modulate cell-surface signalling events by the proteolytic release of soluble forms of proligands for cellular receptors. Many regulatory pathways affect the ADAM17 sheddase activity, but the mechanisms for the activation are still not clear. We have utilized a cell-based ADAM17 assay to show that thiol isomerases, specifically PDI (protein disulfide isomerase), could be responsible for maintaining ADAM17 in an inactive form. Down-regulation of thiol isomerases, by changes in the redox environment (for instance as elicited by phorbol ester modulation of mitochondrial reactive oxygen species) markedly enhanced ADAM17 activation. On the basis of ELISA binding studies with novel fragment antibodies against ADAM17 we propose that isomerization of the disulfide bonds in ADAM17, and the subsequent conformational changes, form the basis for the modulation of ADAM17 activity. The shuffling of disulfide bond patterns in ADAMs has been suggested by a number of recent adamalysin crystal structures, with distinct disulfide bond patterns altering the relative orientations of the domains. Such a mechanism is rapid and reversible, and the role of thiol isomerases should be investigated further as a potential factor in the redox regulation of ADAM17.

Element-Free Galerkin Modelling of Crack Migration in Composite Laminates

The development of a virtual testing environment, as a cost-effective industrial design tool in the design and analysis of composite structures, requires the need to create models efficiently, as well as accelerate the analysis by reducing the number of degrees of freedom, while still satisfying the need for accurately tracking the evolution of a debond, delamination or crack front. The eventual aim is to simulate both damage initiation and propagation in components with realistic geometrical features, where crack propagation paths are not trivial. Meshless approaches, and the Element-Free Galerkin (EFG) method, are particularly suitable for problems involving changes in topology and have been successfully applied to simulate damage in homogeneous materials and concrete. In this work, the method is utilized to model initiation and mixed-mode propagation of cracks in composite laminates, and to simulate experimentally-observed crack migration which is difficult to model using standard finite element analysis. N

Cell Coverage Optimization for the Multicell Massive MIMO Uplink

We investigate the cell coverage optimization problem for the massive multiple-input multiple-output (MIMO) uplink. By deploying tilt-adjustable antenna arrays at the base stations, cell coverage optimization can become a promising technique which is able to strike a compromise between covering cell-edge users and pilot contamination suppression. We formulate a detailed description of this optimization problem by maximizing the cell throughput, which is shown to be mainly determined by the user distribution within several key geometrical regions. Then, the formulated problem is applied to different example scenarios: for a network with hexagonal shaped cells and uniformly distributed users, we derive an analytical lower bound of the ergodic throughput in the objective cell, based on which, it is shown that the optimal choice for the cell coverage should ensure that the coverage of different cells does not overlap; for a more generic network with sectoral shaped cells and non-uniformly distributed users, we propose an analytical approximation of the ergodic throughput. After that, a practical coverage optimization algorithm is proposed, where the optimal solution can be easily obtained through a simple one-dimensional line searching within a confined searching region. Our numerical results show that the proposed coverage optimization method is able to greatly increase the system throughput in macrocells for the massive MIMO uplink transmission, compared with the traditional schemes where the cell coverage is fixed.

Using a Discrete Hidden Markov Model Kernel for lip-based biometric identification

In this paper, a novel and effective lip-based biometric identification approach with the Discrete Hidden Markov Model Kernel (DHMMK) is developed. Lips are described by shape features (both geometrical and sequential) on two different grid layouts: rectangular and polar. These features are then specifically modeled by a DHMMK, and learnt by a support vector machine classifier. Our experiments are carried out in a ten-fold cross validation fashion on three different datasets, GPDS-ULPGC Face Dataset, PIE Face Dataset and RaFD Face Dataset. Results show that our approach has achieved an average classification accuracy of 99.8%, 97.13%, and 98.10%, using only two training images per class, on these three datasets, respectively. Our comparative studies further show that the DHMMK achieved a 53% improvement against the baseline HMM approach. The comparative ROC curves also confirm the efficacy of the proposed lip contour based biometrics learned by DHMMK. We also show that the performance of linear and RBF SVM is comparable under the frame work of DHMMK.

Geometric optimization on visibility problems: metaheuristic and exact solutions

Os problemas de visibilidade têm diversas aplicações a situações reais. Entre os mais conhecidos, e exaustivamente estudados, estão os que envolvem os conceitos de vigilância e ocultação em estruturas geométricas (problemas de vigilância e ocultação). Neste trabalho são estudados problemas de visibilidade em estruturas geométricas conhecidas como polígonos, uma vez que estes podem representar, de forma apropriada, muitos dos objectos reais e são de fácil manipulação computacional. O objectivo dos problemas de vigilância é a determinação do número mínimo de posições para a colocação de dispositivos num dado polígono, de modo a que estes dispositivos consigam “ver” a totalidade do polígono. Por outro lado, o objectivo dos problemas de ocultação é a determinação do número máximo de posições num dado polígono, de modo a que quaisquer duas posições não se consigam “ver”. Infelizmente, a maior parte dos problemas de visibilidade em polígonos são NP-difíceis, o que dá origem a duas linhas de investigação: o desenvolvimento de algoritmos que estabelecem soluções aproximadas e a determinação de soluções exactas para classes especiais de polígonos. Atendendo a estas duas linhas de investigação, o trabalho é dividido em duas partes. Na primeira parte são propostos algoritmos aproximados, baseados essencialmente em metaheurísticas e metaheurísticas híbridas, para resolver alguns problemas de visibilidade, tanto em polígonos arbitrários como ortogonais. Os problemas estudados são os seguintes: “Maximum Hidden Vertex Set problem”, “Minimum Vertex Guard Set problem”, “Minimum Vertex Floodlight Set problem” e “Minimum Vertex k-Modem Set problem”. São também desenvolvidos métodos que permitem determinar a razão de aproximação dos algoritmos propostos. Para cada problema são implementados os algoritmos apresentados e é realizado um estudo estatístico para estabelecer qual o algoritmo que obtém as melhores soluções num tempo razoável. Este estudo permite concluir que as metaheurísticas híbridas são, em geral, as melhores estratégias para resolver os problemas de visibilidade estudados. Na segunda parte desta dissertação são abordados os problemas “Minimum Vertex Guard Set”, “Maximum Hidden Set” e “Maximum Hidden Vertex Set”, onde são identificadas e estudadas algumas classes de polígonos para as quais são determinadas soluções exactas e/ou limites combinatórios.

Politopo de Birkhoff acíclico

Neste trabalho estabelece-se uma interpreta c~ao geom etrica, em termos da teoria dos grafos, para v ertices, arestas e faces de uma qualquer dimens~ao do politopo de Birkho ac clico, Tn = n(T), onde T e uma arvore com n v ertices. Generaliza-se o resultado obtido por G. Dahl, [18], para o c alculo do di^ametro do grafo G( t n), onde t n e o politopo das matrizes tridiagonais duplamente estoc asticas. Adicionalmente, para q = 0; 1; 2; 3 s~ao obtidas f ormulas expl citas para a contagem do n umero de q faces do politopo de Birkho tridiagonal, t n, e e feito o estudo da natureza geom etrica dessas mesmas faces. S~ao, tamb em, apresentados algoritmos para efectuar contagens do n umero de faces de dimens~ao inferior a de uma dada face do politopo de Birkho ac clico.

Extração e estrutura dos polissacarídeos do resíduo do café com atividade imunoestimuladora

As galactomananas das infusões de café apresentam atividade imunoestimuladora in vitro, sendo esta atividade semelhante à das mananas acetiladas extraídas de Aloe vera. As galactomananas presentes no resíduo de café também possuem atividade imunoestimuladora in vitro quando são parcialmente acetiladas. Como as galactomananas são o componente maioritário do resíduo de café e como o café é um produto de largo consumo a nível mundial, o reaproveitamento deste resíduo como fonte de galactomananas com atividade imunoestimuladora deve ser considerado. Esta dissertação procura dar resposta a duas questões: 1. Quais são as estruturas das galactomananas responsáveis pela atividade imunoestimuladora destes polissacarídeos; e 2. Como é que as galactomananas podem ser extraídas quantitativamente do resíduo de café de modo a serem solúveis em água à temperatura ambiente e, assim, poderem ser utilizadas como ingredientes alimentares com atividade imunoestimuladora. A questão 1 foi respondida pela caracterização estrutural de quatro galactomananas, de três origens: a) as galactomananas das infusões de café e do resíduo que apresentaram atividade imunoestimuladora; b) a galactomanana da goma de alfarroba (LBG), que não apresentou atividade imunoestimuladora; e c) a manana acetilada de Aloe vera, que apresentou atividade imunoestimuladora. Estes polissacarídeos foram submetidos à análise de açúcares e de ligações glicosídicas e a hidrólise por endo-β-D- (1→4)-mananase. Os fragmentos de oligossacarídeos mais pequenos foram ainda analisados por espetrometria de massa por ionização de electrospray e espetrometria de massa tandem. As galactomananas das infusões de café, do resíduo de café e do Aloe vera apresentaram grau de ramificação e peso molecular semelhantes, enquanto as galactomananas da LBG apresentaram grau de ramificação e de polimerização maiores. Todas as galactomananas apresentaram resíduos de arabinose como ramificação. O grau de acetilação das galactomananas da LBG foi vestigial enquanto as galactomananas do Aloe vera apresentaram um grau de acetilação de 2,08; para as galactomananas do resíduo de café o grau de acetilação foi de 0,98 e para as infusões foi de 0,08. A localização dos grupos acetilo foi irregular em todos os polímeros. Os resultados obtidos permitem inferir que baixos níveis de ramificação, cadeias pequenas e alguma acetilação parecem promover a atividade imunoestimuladora atribuída às galactomananas. Para responder à questão 2, foi testada uma metodologia que envolveu a torra do resíduo de café a 160 ºC e a 220 ºC e a sua extração com água quente e com soluções de 4 M NaOH à temperatura de 20, 60 e 120 ºC. A torra do resíduo a 160 ºC e a extração sequencial permitiu extrair 56% das galactomananas presentes no resíduo de café e, simultaneamente, 54% das arabinogalactanas. As galactomananas mantiveram a sua estrutura caraterística de polissacarídeo acetilado composto por uma cadeira principal de resíduos de manose em ligação β-(1→4) e resíduos de Gal e Ara nas cadeias laterais. A 220 ºC, as galactomananas foram parcialmente degradadas e o rendimento de extração foi muito menor do que a 160 ºC. No entanto, mesmo a esta temperatura as galactomananas apresentaram resíduos acetilados e a presença de pentoses nas cadeias laterais, o que permite inferir a elevada resistência destes polissacarídeos à temperatura e aos reagentes alcalinos. De forma a melhor compreender a estabilidade térmica das galactomananas do resíduo de café e a influência que a presença de arabinogalactanas pode ter na sua estabilidade, foi feita uma análise termogravimétrica aos polissacarídeos extraídos do resíduo de café assim como a polissacarídeos relacionados estruturalmente com estes, como a celulose, a galactomanana de LBG e a goma arábica, uma arabinogalactana. As galactomananas são termicamente estáveis durante 3 h a 200 ºC, enquanto as arabinogalactanas são estáveis a 180 ºC. De acordo com os perfis dos termogramas obtidos, e pelo cálculo das energias de ativação da degradação térmica, o resíduo de café apresenta uma estabilidade térmica menor do que a galactomanana, possivelmente devido à presença de arabinogalactanas. Apesar de não se ter verificado alterações no termograma da galactomanana do café submetida a um tratamento térmico de 200 ºC durante 3 h, verificam-se alterações estruturais que envolvem a formação de novas ligações glicosídicas, nomeadamente, a formação de resíduos de manose ligados em O-2 e em O-6, reações de transglicosilação, despolimerização, formação de resíduos de anidro-hexoses no terminal redutor e isomerização manose-glucose. Estas alterações promovem a solubilização das galactomananas. Os resultados obtidos permitem propor que o resíduo de café possa ser submetido a uma torra seguida de extração com reagentes alcalinos a quente para obtenção das galactomananas com rendimentos elevados. Estes polissacarídeos podem tornar-se solúveis em água após tratamento térmico a 200 ºC, permitindo assim a sua utilização em formulações alimentares, nomeadamente, por preparação de compostos acetilados com baixos níveis de ramificação e cadeias pequenas de modo a promover a sua atividade imunoestimuladora.