Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold.

Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies

How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results

Geometry of Molecular Motions in Dye Monolayers at Various Coverages

Molecular motion in monolayers is thought to influence the kinetics of charge transport and recombination in systems such as dye-sensitized solar cells (DSSCs). In this work, we use ab initio molecular dynamics to evaluate the geometry and time scale of such molecular motion in a D102 monolayer. D102, a dye that is routinely used in DSSCs, contains two chemical groups, namely, indoline and triphenylethylene, that are also present in many other dyes. We find that, at low surface coverage, the dye molecule exhibits two main tilting axes around which it heavily distorts within 10 ps. Further, the two benzene rings in the triphenylethylene group rotate with a 3–4-ps period. We observe that these large-amplitude movements are suppressed at full coverage, meaning that dye molecules in a monolayer are locked into place and undergo only minor conformational changes. Our observations indicate that, counterintuitively, charge diffusion across dye monolayers might be faster in the parts of the system that are characterized by a lower surface coverage. Because charge transport in dye monolayers has been shown to accelerate recombination kinetics in DSSCs, these results provide the basis for a new understanding of the electronic properties of sensitized systems and device efficiency.National Science Foundation (U.S.) (Grant CHE-1464804

Quantum chemical approaches to [NiFe] hydrogenase

The mechanism by which [NiFe] hydrogenase catalyses the oxidation of molecular hydrogen is a significant yet challenging topic in bioinorganic chemistry. With far-reaching applications in renewable energy and carbon mitigation, significant effort has been invested in the study of these complexes. In particular, computational approaches offer a unique perspective on how this enzyme functions at an electronic and atomistic level. In this article, we discuss state-of-the art quantum chemical methods and how they have helped deepen our comprehension of [NiFe] hydrogenase. We outline the key strategies that can be used to compute the (i) geometry, (ii) electronic structure, (iii) thermodynamics and (iv) kinetic properties associated with the enzymatic activity of [NiFe] hydrogenase and other bioinorganic complexes

L'autonomie des salariés au regard de l'introduction des TIC dans la formation à distance

Avec l'avènement du numérique, de nouveaux défis s'inscrivent dans l'histoire de la formation qui rencontre aujourd'hui un véritable tournant. En offrant de nouvelles perspectives aux salariés, sous le discours d'une plus grande adaptabilité, il s'agit dans cet article de voir si le recours aux outils de communication permet d'accorder une plus grande autonomie aux salariés en formation à distance (FAD). Les salariés parviennent-ils à agir librement, à s'autoréguler dans un espace virtuel supposant réflexions et interactions ? S'appuyant sur les résultats d'une enquête qualitative menée auprès de huit personnes en activité professionnelle, cet article propose de repenser le concept d'autonomie dans les nouvelles modalités de formation distanciée. Les résultats mettent en avant deux dimensions : l'autonomie est favorisée par la liberté d'action mais elle induit de l'isolement