Pd-catalyzed enantioselective aerobic oxidation of secondary alcohols: Applications to the total synthesis of alkaloids

Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described

Precursors of Cytochrome Oxidase in Cytochrome-Oxidase-Deficient Cells of Neurospora crassa

Three different cell types of Neurospora crassa deficient in cytochrome oxidase were studied: the nuclear mutant cni-1, the cytoplasmic mutant mi-1 and copper-depleted wild-type cells. * 1. The enzyme-deficient cells have retained a functioning mitochondrial protein synthesis. It accounted for 12–16% of the total protein synthesis of the cell. However, the analysis of mitochondrial translation products by gel electrophoresis revealed that different amounts of individual membrane proteins were synthesized. Especially mutant cni-1 produced large amounts of a small molecular weight translation product, which is barely detectable in wild-type. * 2. Mitochondrial preparations of cytochrome-oxidase-deficient cells were examined for precursors of cytochrome oxidase. The presence of polypeptide components of cytochrome oxidase in the mitochondria was established with specific antibodies. On the other hand, no significant amounts of heme a could be extracted. * 3. Radioactively labelled components of cytochrome oxidase were isolated by immunoprecipitation and analysed by gel electrophoresis. All three cell types contained the enzyme components 4–7, which are translated on cytoplasmic ribosomes. The mitochondrially synthesized components 1–3 were present in mi-1 mutant and in copper-depleted wild-type cells. In contrast, components 2 and 3 were not detectable in the nuclear mutant cni-1. Both relative and absolute amounts of these polypeptides in the enzyme-deficient cells were quite different from those in wild-type cells. * 4. The components of cytochrome oxidase found in the enzyme-deficient cells were tightly associated with the mitochondrial membranes. * 5. Processes, which affect and may control the production of enzyme precursors or their assembly to a functional cytochrome oxidase are discussed

Magnetization Jump in a Model for Flux Lattice Melting at Low Magnetic Fields

Using a frustrated XY model on a lattice with open boundary conditions, we numerically study the magnetization change near a flux lattice melting transition at low fields. In both two and three dimensions, we find that the melting transition is followed at a higher temperature by the onset of large dissipation associated with the zero-field XY transition. It is characterized by the proliferation of vortex-antivortex pairs (in 2D) or vortex loops (in 3D). At the upper transition, there is a sharp increase in magnetization, in qualitative agreement with recent local Hall probe experiments.Comment: updated figures and texts. new movies available at http://www.physics.ohio-state.edu:80/~ryu/jj.html. Accepted for publication in Physical Review Letter

Quantitative morphometrical characterization of human pronuclear zygotes

BACKGROUND Identification of embryos with high implantation potential remains a challenge in in vitro fertilization (IVF). Subjective pronuclear (PN) zygote scoring systems have been developed for that purpose. The aim of this work was to provide a software tool that enables objective measuring of morphological characteristics of the human PN zygote. METHODS A computer program was created to analyse zygote images semi-automatically, providing precise morphological measurements. The accuracy of this approach was first validated by comparing zygotes from two different IVF centres with computer-assisted measurements or subjective scoring. Computer-assisted measurement and subjective scoring were then compared for their ability to classify zygotes with high and low implantation probability by using a linear discriminant analysis. RESULTS Zygote images coming from the two IVF centres were analysed with the software, resulting in a series of precise measurements of 24 variables. Using subjective scoring, the cytoplasmic halo was the only feature which was significantly different between the two IVF centres. Computer-assisted measurements revealed significant differences between centres in PN centring, PN proximity, cytoplasmic halo and features related to nucleolar precursor bodies distribution. The zygote classification error achieved with the computer-assisted measurements (0.363) was slightly inferior to that of the subjective ones (0.393). CONCLUSIONS A precise and objective characterization of the morphology of human PN zygotes can be achieved by the use of an advanced image analysis tool. This computer-assisted analysis allows for a better morphological characterization of human zygotes and can be used for classificatio

Spin glass behavior of frustrated 2-D Penrose lattice in the classical planar model

Via extensive Monte Carlo studies we show that the frustrated XY Hamiltonian on a 2-D Penrose lattice admits of a spin glass phase at low temperature. Studies of the Edwards-Anderson order parameter, spin glass susceptibility, and local (linear) susceptibility point unequivocally to a paramagnetic to spin glass transition as the temperature is lowered. Specific heat shows a rounded peak at a temperature above the spin glass transition temperature, as is commonly observed in spin glasses. Our results strongly suggest that the critical point exponents are the same as obtained by Bhatt and Young in the ${\pm}J$ Ising model on a square lattice. However, unlike in the latter case, the critical temperature is clearly finite (nonzero). The results imply that a quasiperiodic 2-D array of superconducting grains in a suitably chosen transverse magnetic field should behave as a superconducting glass at low temperature.Comment: RevTex, 4 pages Including 4 figures. To appear in the June 1 1996 issue of Phys. Rev. B (Rapid Communications). Revised/replaced edition contains an erratum at the end of the paper, also to appear in Phys. Rev.

Indication of Superconductivity at 35 K in Graphite-Sulfur Composites

We report magnetization measurements performed on graphite--sulfur composites which demonstrate a clear superconducting behavior below the critical temperature T$_{c0}$ = 35 K. The Meissner-Ochsenfeld effect, screening supercurrents, and magnetization hysteresis loops characteristic of type-II superconductors were measured. The results indicate that the superconductivity occurs in a small sample fraction, possibly related to the sample surface.Comment: published versio

Stability of vortex lines in liquid 3He-4He mixtures at zero temperature

At low temperatures and 3He concentrations below 6.6 %, there is experimental evidence about the existence in liquid helium mixtures, of stable vortices with 3He-rich cores. When the system is either supersaturated or submitted to a tensile strength, vortices lose stability becoming metastable and eventually completely unstable, so that their cores freely expand. Within a density functional approach, we have determined the pressure-3He concentration curve along which this instability appears at zero temperature.Comment: Typeset using Revtex, 9 pages and 5 Postscript figure

The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 °C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones