Isomer‐dependent properties of poly(vinyl pyridine)‐based films grown on copper surfaces

The effect of poly(2‐vinyl pyridine) (P2VP) and poly(4‐vinyl pyridine) (P4VP) isomers on the growth of surface films on copper substrates was studied by electrochemical, spectroscopic, thermogravimentric, and microscopic methods. In acid environment (3% v/v acetic acid) and in the presence of KSCN, electrochemically generated copper cations reacted rapidly with SCN^? and P2VP or P4VP, yielding coordination compounds, which deposited onto copper surfaces as films. The characteristics of such polymer–metal complexes (films) were markedly isomer‐dependent. Cu(I)/P2VP/SCN^? complexes with monovalent cations and sulfur‐coordinated thiocyanate were obtained in the presence of P2VP, whereas the formation of Cu(II)/P4VP/SCN^? complexes with divalent cations and nitrogen‐coordinated thiocyanate was observed in the presence of P4VP. Interestingly, similar physical–chemical properties (electronic structure, stoichiometry, and thermal behavior) were observed for materials synthesized by electrochemical and chemical methods. These results suggest, therefore, that control over the surface properties of copper substrates can be achieved using electrosynthesized films based on different PVP isomers. Besides acting as effective protective barriers against aggressive media and thus reducing the metal dissolution (corrosion) kinetics, these materials are potentially attractive for other applications in which surface properties are paramount, such as in catalysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 215–225, 2009     

Dark energy versus modified gravity

There is now strong observational evidence that the expansion of the Universe is accelerating. The standard explanation invokes an unknown "dark energy" component. But such scenarios are faced with serious theoretical problems, which has led to increased interest in models where instead general relativity is modified in a way that leads to the observed accelerated expansion. The question then arises whether the two scenarios can be distinguished. Here we show that this may not be so easy, demonstrating explicitly that a generalized dark energy model can match the growth rate of the Dvali-Gabadadze-Porrati model and reproduce the 3+1 dimensional metric perturbations. Cosmological observations are then unable to distinguish the two cases.     

Small strain and moderate rotation

Kinematical assumptions leading to the approximate theory of small strain accompanied by moderate rotations are discussed with reference to a three-dimensional continuous body. In particular, the relationship with Korn's inequality is examined. It is found that for bounded bodies the coincidence of small strain and moderate rotation on subsets of non-zero volume measure is not possible. Two explicit examples are presented to illustrate this point.     

Stick-slip instability analysis

A theoretical investigation of friction-induced self-excited oscillations for systems with one degree of freedom is proposed. The friction force is assumed as an odd function of the relative sliding velocity with a jump discontinuity at a value of zero for the relative sliding velocity. The friction characteristic is approximated with a piecewise linear function, i.e. straight line segments with a suitable slope. For the generic system belonging to the class in question, the stick-slip instability region is located on a suitable dimensionless map.

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Sommario Viene proposta un'indagine teorica sulle oscillazioni autoeccitate indotte dall'attrito per sistemi ad un grado di libertà. La forza d'attrito viene assunta come funzione dispari della velocità relativa tra le superfici accoppiate, con una discontinuità di prima specie in corrispondenza del valore nullo della velocità. La caratteristica d'attrito viene approssimata mediante una funzione lineare a tratti con segmenti di opportuna pendenza. Per il generico sistema appartenente alla classe in esame, si perviene all'individuazione, su opportuna mappa adimensionale, della regione di instabilità da stick-slip.

     

A discrete 3D model for bridge aerodynamics and aeroelasticity: nonlinearities and linearizations

A framework for the numerical analysis of bridges under wind excitation is outlined. It is based on structural finite element scheme and cross-sectional wind load models. Two aspects are investigated: (1) how considering the mean steady configuration in the aerodynamic stability calculation; and (2) the effects of load nonlinearities on structural response. A quasi-steady load model is adopted, which is able to deal with the considered problems by using experimental data easily available in the practice. By means of numerical examples, it is pointed out (1) that both the modifications in structural tangential stiffness and in the aerodynamic coefficients due to the mean steady deformation may affect the aeroelastic stability threshold and (2) that load linearization may produce an underestimation of the structural response.     

Mixture models for ordinal responses to account for uncertainty of choice

In CUB models the uncertainty of choice is explicitly modelled as a Combination of discrete Uniform and shifted Binomial random variables. The basic concept to model the response as a mixture of a deliberate choice of a response category and an uncertainty component that is represented by a uniform distribution on the response categories is extended to a much wider class of models. The deliberate choice can in particular be determined by classical ordinal response models as the cumulative and adjacent categories model. Then one obtains the traditional and flexible models as special cases when the uncertainty component is irrelevant. It is shown that the effect of explanatory variables is underestimated if the uncertainty component is neglected in a cumulative type mixture model. Visualization tools for the effects of variables are proposed and the modelling strategies are evaluated by use of real data sets. It is demonstrated that the extended class of models frequently yields better fit than classical ordinal response models without an uncertainty component.     

Development of small molecule inhibitors and probes of human SUMO deconjugating proteases

Sentrin specific proteases (SENPs) are responsible for activating and deconjugating SUMO (Small Ubiquitin like MOdifier) from target proteins. It remains difficult to study this posttranslational modification due to the lack of reagents that can be used to block the removal of SUMO from substrates. Here, we describe the identification of small molecule SENP inhibitors and active site probes containing aza-epoxide and acyloxymethyl ketone (AOMK) reactive groups. Both classes of compounds are effective inhibitors of hSENPs 1, 2, 5, and 7 while only the AOMKs efficiently inhibit hSENP6. Unlike previous reported peptide vinyl sulfones, these compounds covalently labeled the active site cysteine of multiple recombinantly expressed SENP proteases and the AOMK probe showed selective labeling of these SENPs when added to complex protein mixtures. The AOMK compound therefore represents promising new reagents to study the process of SUMO deconjugation.     

Determination of the geographical origin of Brazilian wines by isotope and mineral analysis

In the present research, we studied wines from three different south Brazilian winemaking regions with the purpose of differentiating them by geographical origin of the grapes. Brazil's wide territory and climate diversity allow grape cultivation and winemaking in many regions of different and unique characteristics. The wine grape cultivation for winemaking concentrates in the South Region, mainly in the Serra Gaúcha, the mountain area of the state of Rio Grande do Sul, which is responsible for 90% of the domestic wine production. However, in recent years, two new production regions have developed: the Campanha, the plains to the south and the Serra do Sudeste, the hills to the southeast of the state. Analysis of isotopic ratios of ¹⁸O/¹⁶O of wine water, ¹³C/¹²C of ethanol, and of minerals were used to characterize wines from different regions. The isotope analysis of δ¹⁸O of wine water and minerals Mg and Rb were the most efficient to differentiate the regions. By using isotope and mineral analysis, and discrimination analysis, it was possible to classify the wines from south Brazil.