Topologically invariant reaction coordinates for simulating multistate chemical reactions.

Evaluating free energy profiles of chemical reactions in complex environments such as solvents and enzymes requires extensive sampling, which is usually performed by potential of mean force (PMF) techniques. The reliability of the sampling depends not only on the applied PMF method but also the reaction coordinate space within the dynamics is biased. In contrast to simple geometrical collective variables that depend only on the positions of the atomic coordinates of the reactants, the E(gap) reaction coordinate (the energy difference obtained by evaluating a suitable force field using reactant and product state topologies) has the unique property that it is able to take environmental effects into account leading to better convergence, a more faithful description of the transition state ensemble and therefore more accurate free energy profiles. However, E(gap) requires predefined topologies and is therefore inapplicable for multistate reactions, in which the barrier between the chemically equivalent topologies is comparable to the reaction activation barrier, because undesired "side reactions" occur. In this article, we introduce a new energy-based collective variable by generalizing the E(gap) reaction coordinate such that it becomes invariant to equivalent topologies and show that it yields more well behaved free energy profiles than simpler geometrical reaction coordinates.

Fracture mechanics of idealised bituminous mixes

© 2014 Taylor & Francis. The durability of asphalt pavements is strongly impaired by cracks, caused primarily by traffic loads and environmental effects. In this work, fracture behaviour of idealised asphalt mixes is investigated. Experiments on idealised asphalt mixes under pure-tension mode (mode I cracking) were performed and fracture parameters were evaluated. In these three-point bend fracture tests, the test variables were temperature and load rate. The test data were stored in an asphalt materials database and special-purpose tools were implemented to analyse and handle the laboratory data automatically. Fracture mechanism maps were constructed, showing the conditions associated with ductile, brittle and ductile-brittle transition regimes of behaviour. The mechanism maps show the failure response of the material in terms of the stress intensity factor, strain energy release rate and J-integral as a function of the temperature-compensated crack mouth opening strain rate. Fracture behaviour of asphalt mix specimens was simulated by cohesive zone model in conjunction with a novel material constitutive model for asphalt mixes. The finite element model agrees well with the experimental results and provides insights into fracture response of the notched asphalt mix beam specimens.

Effects of solution exposure on the combined axial-shear behaviour of unidirectional CFRP rods

In fibre reinforced polymer (FRP) prestressed concrete applications, an FRP tendon must sustain high axial tensile stresses and, if cracks occur, additional dowel forces. The tendon may also be exposed to solutions and so the combined axial-shear stress performance after long-term environmental exposure is important. Experiments were conducted to investigate the combined axial-shear stress failure envelope for unidirectional carbon FRP tendons which had been exposed to either water, salt water or concrete pore solution at 60 °C for approximately 18 months. The underlying load resisting mechanisms were found to depend on the loading configuration, restraint effects and the initial stress state. When saturated, CFRP tendons are likely to exhibit a reduced shear stiffness. However, the ultimate limit state appeared to be fibre-dominated and was therefore less susceptible to reductions due to solution uptake effects. © 2012 Elsevier Ltd. All rights reserved.

Anxiety reduction through detachment: subjective, physiological, and neural effects.

The ability to volitionally regulate emotions helps to adapt behavior to changing environmental demands and can alleviate subjective distress. We show that a cognitive strategy of detachment attenuates subjective and physiological measures of anticipatory anxiety for pain and reduces reactivity to receipt of pain itself. Using functional magnetic resonance imaging, we locate the potential site and source of this modulation of anticipatory anxiety in the medial prefrontal/anterior cingulate and anterolateral prefrontal cortex, respectively.