Single molecule conductance through rigid norbornylogous bridges with zero average curvature

A new homologous series of norbornylogous (NB) bridges has been synthesized in which the average curvature of the bridges is very small. The molecules are rigid and have two thiol moieties at each end to allow them to form self-assembled monolayers (SAMs) and to connect to two gold electrodes to form a molecular junction. The SAMs formed were characterized using electrochemistry to determine the surface coverage of molecules on gold surface and to provide an indication of the packing of the NB bridges while ellipsometry and X-ray photoelectron spectroscopy (XPS) were used to provide an indication of the SAM thickness and orientation. Single molecule conductance of NB bridges was measured as a function of the molecular length. The conductance was found to decrease exponentially with the length with a decay constant that is exactly correlated with photoelectron transfer and other studies at the multiple molecule level. The molecule−electrode contact resistance was determined and compared with that of related alkanedithiol molecular junctions.

Evaluating the stability of disulfide bridges in proteins: a torsional potential energy surface for diethyl disulfide

Disulfide bonds formed by the oxidation of cysteine residues in proteins are the major form of intra- and inter-molecular covalent linkages in the polypeptide chain. To better understand the conformational energetics of this linkage, we have used the MP2(full)/6-31G(d) method to generate a full potential energy surface (PES) for the torsion of the model compound diethyl disulfide (DEDS) around its three critical dihedral angles (χ2, χ3, χ2′). The use of ten degree increments for each of the parameters resulted in a continuous, fine-grained surface. This allowed us to accurately predict the relative stabilities of disulfide bonds in high resolution structures from the Protein Data Bank. The MP2(full) surface showed significant qualitative differences from the PES calculated using the Amber force field. In particular, a different ordering was seen for the relative energies of the local minima. Thus, Amber energies are not reliable for comparison of the relative stabilities of disulfide bonds. Surprisingly, the surface did not show a minimum associated with χ2 − 60°, χ390, χ2′ − 60°. This is due to steric interference between Hα atoms. Despite this, significant populations of disulfides were found to adopt this conformation. In most cases this conformation is associated with an unusual secondary structure motif, the cross-strand disulfide. The relative instability of cross-strand disulfides is of great interest, as they have the potential to act as functional switches in redox processes.

Bridges

Bridges is a hand-drawn film. Some elements have been printed onto clear acatate that has then been glued onto a clear film surface, which itself has been prepared by bleaching away parts of the sound and image of the original film, a documentary about bridges.The sound develops a chant like quality using the rhythm of a race call and a the commentary of a football match. A celebration of the Australian voice.

The silent witness: art as a mode of representation of voices and visions of how,as a woman, I build borders and bridges in enacting my identit(ies)

Feminist theorists unveil how women negotiate their identities within complex entanglements of social constructs such as race, ethnicity, religious belief and practices, cultural tradition, and values. Feminist artists use subjective experiences that shape representation and performativity in empowering women to have a ‘voice’. In this paper, I focus on ‘breaking silences’ through series of my artworks (as part of my PhD research) that represent self-narratives as subjectivities of life experiences, contingencies, and cultural shifts through migration transitions as new ways of figuration and reflection on such issues. I look through discourses of gender differences, nomadic subjectivity, and new ways of figurations (Braidotti 2011, 10) and the affect theory (Gregg and Seigworth 2010), and the concept of giving ‘voice’ (Berlant 2011). Such discourses frame how I interrogate and represent my gendered identities.

Three-dimensional numerical simulation of blood flow in mouse aortic arch around atherosclerotic plaques

Atherosclerosis is a progressive disease, involving the build-up of lipid streaks in artery walls, leading to plaques. Understanding the development of atherosclerosis and plaque vulnerability is critically important since plaque rupture can result in heart attack or stroke. Plaques can be divided into two distinct types: those likely to rupture (vulnerable) or less likely to rupture (stable). In the last decade, researchers have been interested in studying the influence of the mechanical effects (blood shear stress, pressure forces and structural stress) on the plaque formation, progression and rupture processes but no general agreement has been found. The purpose of the present work is to include more realistic conditions for the numerical calculations of the blood flow by implementing real geometries with plaques in the numerical model. Hemodynamical parameters are studied in both diseased and healthy configurations. The healthy configuration is obtained by removing numerically the plaques from three dimensional geometries obtained by micro-computed tomography. A new hemodynamical parameter is also introduced to relate the location of plaques to the characteristics of the flow in the healthy configuration. © 2014 .

Avaliação de opções: o caso brasileiro: utilização de modelos Arch na estimação dos parâmetros

o trabalho se refere à avaliação de opções através do modelo conhecido pelo nome de seus autores, Black-Scholes. É descrito o desenvolvimento da teoria de opções, desde os primórdios da existência de mercados organizados deste derivativo, no século XVII, até os mais importantes trabalhos dos primeiros anos da década de 1990. É destacado o papel fundamental da estimação correta dos parâmetros a serem inseridos no modelo de avaliação. Após esta revisão, um teste do modelo Black-Scholes é realizado no mercado de opções sobre ouro da BM&F, utilizando-se mecanismos tradicionais de estimação dos parâmetros e apurando-se a diferença existente entre o valor dado pelo modelo de avaliação e o observado no mercado. Novos mecanismos de apuração dos parâmetros fundamentais, volatilidade e taxa de juros, são propostos, baseados no comportamento das séries históricas a eles referentes. A análise deste comportamento mostra a adequação destas séries à uma classe de modelos econométricos conhecidos como ARCH - Autorregressive Conditiona! Heterocedasticity Mode! . Três novos testes do modelo Black-Scholes no mercado de opções são realizados: o primeiro usando a volatilidade estimada através de um modelo ARCH(1) e a taxa de juros estimada de forma tradicional, o segundo usando a taxa de juros estimada através de um modelo ARCH-M(1) e a volatilidade estimada de forma tradicional e, finalmente, o terceiro, usando a volatilidade estimada através de um modelo ARCH(1) e a taxa de juros estimada através de um modelo ARCH-M(1). As diferenças, nos três casos, entre os valores dados pelo modelo Black-Scholes e os observados no mercado, foram computadas. Os resultados indicaram que o uso da volatilidade estimada através do modelo ARCH(1) melhora a performance do modelo Black-Scholes, perfomance esta medida pelo erro quadrático médio entre os valores dados pelo modelo e os observados no mercado. O mesmo não ocorreu com a utilização da taxa de juros estimada pelo modelo ARCH-M(1), apesar da compatibilidade teórica apresentada entre a série temporal destas taxas e o modelo. O autor acredita que este resultado seja devido à problemas encontrados na estimação dos parâmetros deste modelo ARCH-M(1). Também a inserção conjunta dos dois parâmetros estimados através dos modelos da classe ARCH não foi frutífera, ainda em função dos problemas de estimação dos modelos referentes à taxa de juros. As conclusões básicas do trabalho indicam que as série temporais em estudo são modeláveis e que os modelos da classe ARCH se apresentam como promissores para este fim, ao menos no que tange à volatilidade.

Estimating and forecasting the volatility of Brazilian finance series using arch models (Preliminary Version)

The goal of this paper is to present a comprehensive emprical analysis of the return and conditional variance of four Brazilian …nancial series using models of the ARCH class. Selected models are then compared regarding forecasting accuracy and goodness-of-…t statistics. To help understanding the empirical results, a self-contained theoretical discussion of ARCH models is also presented in such a way that it is useful for the applied researcher. Empirical results show that although all series share ARCH and are leptokurtic relative to the Normal, the return on the US$ has clearly regime switching and no asymmetry for the variance, the return on COCOA has no asymmetry, while the returns on the CBOND and TELEBRAS have clear signs of asymmetry favoring the leverage e¤ect. Regarding forecasting, the best model overall was the EGARCH(1; 1) in its Gaussian version. Regarding goodness-of-…t statistics, the SWARCH model did well, followed closely by the Student-t GARCH(1; 1)

Double aortic arch in a dog (Canis familiaris): a case report

We herein report a case of a double aortic arch in a 10-week-old male dog of no defined race, which presented episodes of regurgitation at the time of weaning. This vascular malformation was Characterized by the persistence of two aortic arches, right and left, of varying dimensions. The right aortic arch was observed to be larger. During post mortem examination the vessels of the animal were injected with coloured latex bi-centrifuged CIS 1-4 polisopreno which revealed the patency of the two aortic arches. Concomitantly, dilation of the cranial oesophagus causing constriction was observed, indicating megaesophagus, Apart from the constriction, the oesophagus presented normal morphometric parameters in relation to its dimensions.