Periplasmic nitrate reductase revisited: a sulfur atom completes the sixth coordination of the catalytic molybdenum

J Biol Inorg Chem. 2008 Jun;13(5):737-53. doi: 10.1007/s00775-008-0359-6

The effect of demand information sharing in a supply chain under demand uncertainty: a simulation study

Dissertação para obtenção do Grau de Mestre em Engenharia e Gestão Industrial

The sovereign CDS-Bond basis: From a crisis perspective

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Finance from the NOVA – School of Business and Economics

Bond fund runs: The financial crisis case

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Finance from the NOVA – School of Business and Economics

Effect of environmental ageing on the numerical response of FRP-strengthened masonry walls

Recent durability studies have shown the susceptibility of bond in fiber-reinforced polymer (FRP) strengthened masonry components to hygrothermal exposures. However, it is not clear how this local material degradation affects the global behavior of FRP-strengthened masonry structures. This study addresses this issue by numerically investigating the nonlinear behavior of FRP-masonry walls after aging in two different environmental conditions. A numerical modeling strategy is adopted and validated with existing experimental tests on FRP-strengthened masonry panels. The model, once validated, is used for modeling of four hypothetical FRP-strengthened masonry walls with different boundary conditions, strengthening schemes, and reinforcement ratios. The nonlinear behavior of the walls is then simulated before and after aging in two different environmental conditions. The degradation data are taken from previous accelerated aging tests. The changes in the failure mode and nonlinear response of the walls after aging are presented and discussed.

Moisture-induced degradation of interfacial bond in FRP-strengthened masonry

Externally bonded strengthening of masonry structures using Fiber Reinforced Polymers (FRPs) has been accepted as a promising technique. Although the effectiveness of FRPs in improving the performance of masonry components has been extensively investigated, their long-term performance and durability remain poorly addressed. This paper, tackling one of the aspects related to durability of these systems, presents an experimental investigation on the effect of long-term (one year) water immersion on the performance of GFRP-strengthened bricks. The tests include materials' mechanical tests, as well as pull-off and single-lap shear bond tests, to investigate the changes in material properties and bond behavior with immersion time, respectively. The effect of mechanical surface treatment on the durability of the strengthened system as well as the reversibility of the degradation upon partial drying are also investigated. The experimental results are presented and critically discussed.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Effect of sodium chloride on solutesolvent interactions in aqueous polyethylene glycolsodium sulfate two-phase systems

Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000sodium sulfate0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solutesolvent interactions. The results obtained in the study show that solutesolvent interactions of nonionic organic compounds and proteins in polyethylene glycolsodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Leadership and overcoming coordination failure with asymmetric costs

We study how the heterogeneity of agents affects the extent to which changes in financial incentives can pull a group out of a situation of coordination failure. We focus on the connections between cost asymmetries and leadership. Experimental subjects interact in groups of four in a series of weak-link games. The treatment variable is the distribution of high and low effort cost across subjects. We present data for one, two and three low-cost subjects as well as control sessions with symmetric costs. The overall pattern of coordination improvement is common across treatments. Early coordination improvements depend on the distribution of high and low effort costs across subjects, but these differences disappear with time. We find that initial leadership in overcoming coordination failure is not driven by low-cost subjects but by subjects with the most frequent cost. This conformity effect can be due to a kind of group identity or to the cognitive simplicity of acting with identical others.

Pooling of dentin microtensile bond strength data improves clinical correlation.

Purpose: To evaluate whether the correlation between in vitro bond strength data and estimated clinical retention rates of cervical restorations after two years depends on pooled data obtained from multicenter studies or single-test data. Materials and Methods: Pooled mean data for six dentin adhesive systems (Adper Prompt L-Pop, Clearfil SE, OptiBond FL, Prime & Bond NT, Single Bond, and Scotchbond Multipurpose) and four laboratory methods (macroshear, microshear, macrotensile and microtensile bond strength test) (Scherrer et al, 2010) were correlated to estimated pooled two-year retention rates of Class V restorations using the same adhesive systems. For bond strength data from a single test institute, the literature search in SCOPUS revealed one study that tested all six adhesive systems (microtensile) and two that tested five of the six systems (microtensile, macroshear). The correlation was determined with a database designed to perform a meta-analysis on the clinical performance of cervical restorations (Heintze et al, 2010). The clinical data were pooled and adjusted in a linear mixed model, taking the study effect, dentin preparation, type of isolation and bevelling of enamel into account. A regression analysis was carried out to evaluate the correlation between clinical and laboratory findings. Results: The results of the regression analysis for the pooled data revealed that only the macrotensile (adjusted R2 = 0.86) and microtensile tests (adjusted R2 = 0.64), but not the shear and the microshear tests, correlated well with the clinical findings. As regards the data from a single-test institute, the correlation was not statistically significant. Conclusion: Macrotensile and microtensile bond strength tests showed an adequate correlation with the retention rate of cervical restorations after two years. Bond strength tests should be carried out by different operators and/or research institutes to determine the reliability and technique sensitivity of the material under investigation.

Calorimetry of dehydrogenation and dangling-bond recombination in several hydrogenated amorphous silicon materials

Differential scanning calorimetry (DSC) was used to study the dehydrogenation processes that take place in three hydrogenated amorphous silicon materials: nanoparticles, polymorphous silicon, and conventional device-quality amorphous silicon. Comparison of DSC thermograms with evolved gas analysis (EGA) has led to the identification of four dehydrogenation processes arising from polymeric chains (A), SiH groups at the surfaces of internal voids (A'), SiH groups at interfaces (B), and in the bulk (C). All of them are slightly exothermic with enthalpies below 50 meV/H atoms , indicating that, after dissociation of any SiH group, most dangling bonds recombine. The kinetics of the three low-temperature processes [with DSC peak temperatures at around 320 (A),360 (A'), and 430°C (B)] exhibit a kinetic-compensation effect characterized by a linea relationship between the activation entropy and enthalpy, which constitutes their signature. Their Si-H bond-dissociation energies have been determined to be E (Si-H)0=3.14 (A), 3.19 (A'), and 3.28 eV (B). In these cases it was possible to extract the formation energy E(DB) of the dangling bonds that recombine after Si-H bond breaking [0.97 (A), 1.05 (A'), and 1.12 (B)]. It is concluded that E(DB) increases with the degree of confinement and that E(DB)>1.10 eV for the isolated dangling bond in the bulk. After Si-H dissociation and for the low-temperature processes, hydrogen is transported in molecular form and a low relaxation of the silicon network is promoted. This is in contrast to the high-temperature process for which the diffusion of H in atomic form induces a substantial lattice relaxation that, for the conventional amorphous sample, releases energy of around 600 meV per H atom. It is argued that the density of sites in the Si network for H trapping diminishes during atomic diffusion

Stochastic stability and the evolution of coordination in spatially structured populations.

Animals can often coordinate their actions to achieve mutually beneficial outcomes. However, this can result in a social dilemma when uncertainty about the behavior of partners creates multiple fitness peaks. Strategies that minimize risk ("risk dominant") instead of maximizing reward ("payoff dominant") are favored in economic models when individuals learn behaviors that increase their payoffs. Specifically, such strategies are shown to be "stochastically stable" (a refinement of evolutionary stability). Here, we extend the notion of stochastic stability to biological models of continuous phenotypes at a mutation-selection-drift balance. This allows us to make a unique prediction for long-term evolution in games with multiple equilibria. We show how genetic relatedness due to limited dispersal and scaled to account for local competition can crucially affect the stochastically-stable outcome of coordination games. We find that positive relatedness (weak local competition) increases the chance the payoff dominant strategy is stochastically stable, even when it is not risk dominant. Conversely, negative relatedness (strong local competition) increases the chance that strategies evolve that are neither payoff nor risk dominant. Extending our results to large multiplayer coordination games we find that negative relatedness can create competition so extreme that the game effectively changes to a hawk-dove game and a stochastically stable polymorphism between the alternative strategies evolves. These results demonstrate the usefulness of stochastic stability in characterizing long-term evolution of continuous phenotypes: the outcomes of multiplayer games can be reduced to the generic equilibria of two-player games and the effect of spatial structure can be analyzed readily.

Ex post bargaining, labor coordination and wage formation at the firm level

We lay out a model of wage bargaining with two leading features:bargaining is ex post to relevant investments and there isindividual bargaining in firms without a Union. We compareindividual ex post bargaining to coordinated ex post bargainingand we analyze the effects on wage formation. As opposed to exante bargaining models, the costs of destroying the employmentrelationship play a crucial role in determining wages. Highfiring costs in particular yield a rent for employees. Ourtheory points to a employer size-wage effect that is independentof the production function and market power. We derive a simpleleast squares specification from the theoretical model thatallow us to estimate components of the wage premium fromcoordination. We reject the hypothesis that labor coordinationdoes not alter the extensive form of the bargaining game. Laborcoordination substantially increases bargaining power butdecreases labor's ability to pose costly threats to the firm.

Effect of different warm-up strategies on simulated laparoscopy performance: a randomized controlled trial.

OBJECTIVE: The objective of this trial was to assess which type of warm-up has the highest effect on virtual reality (VR) laparoscopy performance. The following warm-up strategies were applied: a hands-on exercise (group 1), a cognitive exercise (group 2), and no warm-up (control, group 3). DESIGN: This is a 3-arm randomized controlled trial. SETTING: The trial was conducted at the department of surgery of the University Hospital Basel in Switzerland. PARTICIPANTS: A total of 94 participants, all laypersons without any surgical or VR experience, completed the study. RESULTS: A total of 96 participants were randomized, 31 to group 1, 31 to group 2, and 32 to group 3. There were 2 postrandomization exclusions. In the multivariate analysis, we found no evidence that the intervention had an effect on VR performance as represented by 6 calculated subscores of accuracy, time, and path length for (1) camera manipulation and (2) hand-eye coordination combined with 2-handed maneuvers (p = 0.795). Neither the comparison of the average of the intervention groups (groups 1 and 2) vs control (group 3) nor the pairwise comparisons revealed any significant differences in VR performance, neither multivariate nor univariate. VR performance improved with increasing performance score in the cognitive exercise warm-up (iPad 3D puzzle) for accuracy, time, and path length in the camera navigation task. CONCLUSIONS: We were unable to show an effect of the 2 tested warm-up strategies on VR performance in laypersons. We are currently designing a follow-up study including surgeons rather than laypersons with a longer warm-up exercise, which is more closely related to the final task.