Water exchange of a ProHance MRI contrast agent: isomer-dependent free-energy landscapes and mechanisms

The water-exchange reaction in two diastereoisomers of the clinical magnetic resonance imaging contrast agent [Gd(HP-DO3A)(H(2)O)] (also known as ProHance) has been studied using ab initio simulations. On the basis of the molecular-level details of the mechanism derived from these simulations in aqueous solution, we unravel the underlying difference in the free energies and mechanisms of water exchange in the two diastereoisomers. These findings reveal the crucial role played by hydrogen-bonding dynamics and thus suggest their appropriate control in tailoring improved gadolinium-based constrast agents.     

(Li/Ag)CoO2: a new intergrowth cobalt oxide composed of rock salt and delafossite layers

A new ordered (Li/Ag)CoO(2) layered compound with an unusual oxygen packing combining rock salt and delafossite layers is obtained during the (Li(+), Na(+))/Ag(+) ionic exchange from the OP4-(Li/Na)CoO(2) precursor. This compound is actually an intermediate step to the final D4-AgCoO(2) delafossite and can be isolated thanks to the kinetics difference between the Li(+)/Ag(+) and Na(+)/Ag(+) exchange processes. It crystallizes in the P6(3)/mmc space group with cell parameters a(hex.) = 2.848(3) ? and c(hex.) = 21.607(7) ?. The details of the structure as well as its thermal stability and transport properties are presented and discussed.     

Thermodynamics of the 3D Hubbard model on approaching the Néel transition

We study the thermodynamic properties of the 3D Hubbard model for temperatures down to the Néel temperature by using cluster dynamical mean-field theory. In particular, we calculate the energy, entropy, density, double occupancy, and nearest-neighbor spin correlations as a function of chemical potential, temperature, and repulsion strength. To make contact with cold-gas experiments, we also compute properties of the system subject to an external trap in the local density approximation. We find that an entropy per particle S/N ≈ 0.65(6) at U/t = 8 is sufficient to achieve a Néel state in the center of the trap, substantially higher than the entropy required in a homogeneous system. Precursors to antiferromagnetism can clearly be observed in nearest-neighbor spin correlators.     

Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts

A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.     

Fate of vacancy-induced supersolidity in 4He

The supersolid state of matter, exhibiting nondissipative flow in solids, has been elusive for 35 years. The recent discovery of a nonclassical moment of inertia in solid 4He by Kim and Chan provided the first experimental evidence, although the interpretation in terms of supersolidity of the ideal crystal phase remains a subject to debate. Using quantum Monte Carlo methods we investigate the long-standing question of vacancy-induced superflow and find that vacancies in a 4He crystal phase separate instead of forming a supersolid. On the other hand, nonequilibrium vacancies relaxing on defects of polycrystalline samples could provide an explanation for the experimental observations.     

ChemInform Abstract: Reinvestigation of the OP4-(Li/Na)CoO2-Layered System and First Evidence of the (Li/Na/Na)CoO2 Phase with OPP9 Oxygen Stacking.

The metastable 1:1 Li/Na-stacked OP4-Li_0.42Na_0.37CoO₂ phase is synthesized from a mixture of O3-LiCoO₂ and P2-Na_0.7CoO₂ in a molar ratio of 42:58 (sealed gold tubes, 920 °C, 24 h, very fast quenching).