Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones

This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.     

Enantioselective conjugate radical addition to alpha'-hydroxy enones

Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It has been found that radical additions to alpha'-hydroxy alpha,beta-unsaturated ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding the addition products in high chemical yields and good enantiomeric excesses.     

Crystallization kinetics and excess free energy of H2O and D2O nanoscale films of amorphous solid water

Temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) are used to investigate the crystallization kinetics and measure the excess free energy of metastable amorphous solid water films (ASW) of H(2)O and D(2)O grown using molecular beams. The desorption rates from the amorphous and crystalline phases of ASW are distinct, and as such, crystallization manifests can be observed in the TPD spectrum. The crystallization kinetics were studied by varying the TPD heating rate from 0.001 to 3 K/s. A coupled desorption-crystallization kinetic model accurately simulates the desorption spectra and accurately predicts the observed temperature shifts in the crystallization. Isothermal crystallization studies using RAIRS are in agreement with the TPD results. Furthermore, highly sensitive measurements of the desorption rates were used to determine the excess free energy of ASW near 150 K. The excess entropy obtained from these data is consistent with there being a thermodynamic continuity between ASW and supercooled liquid water.     

Spectroscopic studies of molybdenum and tungsten enzymes

Molybdenum and tungsten are the only second and third-row transition elements with a known function in living systems. Molybdenum fulfills functional roles in enzyme systems in almost all living creatures, from bacteria through plants to invertebrates and mammals, while tungsten takes the place of molybdenum in some prokaryotes, especially the hyperthermophilic archaea. The enzymes contain the metal bound by an unusual sulfur-containing cofactor. Despite possessing common structural elements, the enzymes are remarkable in the range of different chemical reactions that are catalyzed, although almost all are two-electron oxidation–reduction reactions in which an oxygen atom is transferred to or from the molybdenum. The functional roles filled by molybdenum enzymes are equally diverse; for example, they play essential roles in microbial respiration, in the uptake of nitrogen in green plants, in controlling insect eye color, and in human health. Spectroscopic studies, in particular electron paramagnetic resonance and X-ray absorption spectroscopy, have played an essential role in our understanding of the active site structures and catalytic mechanisms of the molybdenum and tungsten enzymes. This review summarizes the role spectroscopy has played in the state of our knowledge of the molybdenum and tungsten enzymes, with particular regard to structural information on the molybdenum sites.     

Diastereoselective tin-free tandem radical additions to 3-formylchromones

A tin-free tandem radical addition methodology onto 3-formylchromones is presented. This radical process yields functionalized chromone structures via two carbon-carbon bond-forming steps. These products contain up to three contiguous stereocenters with good to excellent dr's and yields.     

Dynamical consequences of a constraint on the Langevin thermostat in molecular cluster simulation

We investigate some unusual behaviour observed while performing molecular dynamics simulations of small molecular clusters using a constrained Langevin thermostat. Atoms appear to be thermalised to different temperatures that depend on their mass and on the total number of particles in the system. The deviation from the zeroth law of thermodynamics can be considerable for small systems of heavy and light particles. We trace this behaviour to the absence of thermal noise acting on the centre of mass of the system. This is demonstrated by solving the stochastic dynamics for the constrained thermostat and comparing the results with simulation data. By removing the constraint, the Langevin thermostat may be restored to its intended behaviour. We also investigate a Langevin thermostat constrained to have zero total force acting on its centre of mass, and find similar deficiencies.     

Curvature of the space of positive Lagrangians

A Lagrangian submanifold in an almost Calabi–Yau manifold is called positive if the real part of the holomorphic volume form restricted to it is positive. An exact isotopy class of positive Lagrangian submanifolds admits a natural Riemannian metric. We compute the Riemann curvature of this metric and show all sectional curvatures are non-positive. The motivation for our calculation comes from mirror symmetry. Roughly speaking, an exact isotopy class of positive Lagrangians corresponds under mirror symmetry to the space of Hermitian metrics on a holomorphic vector bundle. The latter space is an infinite-dimensional analog of the non-compact symmetric space dual to the unitary group, and thus has non-positive curvature.