Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides

The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co-X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co-OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the identification of more active catalysts for the HKR of synthetically useful terminal epoxides.     

Hot dense capsule-implosion cores produced by Z-pinch dynamic Hohlraum radiation

Hot dense capsule implosions driven by Z-pinch x rays have been measured using a approximately 220 eV dynamic Hohlraum to implode 1.7-2.1 mm diameter gas-filled CH capsules. The capsules absorbed up to approximately 20 kJ of x rays. Argon tracer atom spectra were used to measure the T(e) approximately 1 keV electron temperature and the n(e) approximately 1-4 x 10(23) cm(-3) electron density. Spectra from multiple directions provide core symmetry estimates. Computer simulations agree well with the peak emission values of T(e), n(e), and symmetry, indicating reasonable understanding of the Hohlraum and implosion physics.     

Modeling of realistic cladding structures for air-core photonic bandgap fibers

Cladding structures of photonic bandgap fibers often have airholes of noncircular shape, and, typically, close-to-hexagonal airholes with curved corners are observed. We study photonic bandgaps in such structures by aid of a two-parameter representation of the size and curvature. For the fundamental bandgap we find that the bandgap edges (the intersections with the air line) shift toward shorter wavelengths when the air-filling fraction f is increased. The bandgap also broadens, and the relative bandwidth increases exponentially with f2. Compared with recent experiments [Nature 424, 657 (2003)] we find very good agreement.     

Rapidity dependence of charged antihadron to hadron ratios in Au+Au collisions at sqrt[s(NN)]=200 GeV

We present ratios of the numbers of charged antihadrons to hadrons (pions, kaons, and protons) in Au+Au collisions at sqrt[s(NN)]=200 GeV as a function of rapidity in the range y=0-3. While the ratios at midrapidity are approaching unity, the K(-)/K(+) and p;/p ratios decrease significantly at forward rapidities. An interpretation of the results within the statistical model indicates a reduction of the baryon chemical potential from mu(B) approximately 130 MeV at y=3 to mu(B) approximately 25 MeV at y=0.     

Synthesis and evaluation of new potential HIV-1 non-nucleoside reverse transcriptase inhibitors. New analogues of MKC-442 containing Michael acceptors in the C-6 position

Analogues of MKC-442 capable of undergoing Michael addition reactions were synthesised in order to investigate the activity against the HIV-1 mutant (Y181C). An improved activity was postulated on the basis of a possible covalent binding to the mercapto group of Cys181. Lithiation of the C-6 position of 1-ethoxymethyl-5-ethyl-1H-pyrimidine-2,4-dione (5) was followed by reaction with alpha,beta-unsaturated aldehydes and oxidation of the alcohols formed to give the alkenoyl analogues 1a-3a. Analogues 1b-3b containing an allyloxymethyl group in the N-1 position instead of the ethoxymethyl group could not be synthesised due to isomerisation of the allylic group during the metallation reaction. The NMR data for compounds 1a-3a showed a hindered rotation, which was more pronounced for the 6-cyclohexenylcarbonyl derivative 3a than for the propenyl derivatives 1a and 2a. Moderate activity against wild type HIV-1 was observed for the alcohol 8 and the ketones 2a-3a. However, no activity was observed against the Y181C mutant.     

Monosaccharide templates for de novo designed 4-alpha-helix bundle proteins: template effects in carboproteins

De novo design and total chemical synthesis of proteins provide powerful approaches to critically test our understanding of protein folding, structure, and stability. The 4-alpha-helix bundle is a frequently studied structure in which four amphiphilic alpha-helical peptide strands form a hydrophobic core. Assembly of protein models on a template has been suggested as a way to reduce the entropy of folding. We have previously developed the concept of carbohydrates as templates in the de novo design of protein models termed 'carboproteins'. Here we present the chemical synthesis of three 8.1 kDa 4-alpha-helix bundles by oxime ligation of tetra-aminooxyacetyl functionalized D-galacto-, D-gluco-, and D-altropyranoside templates with an amphiphilic C-terminal hexadecapeptide aldehyde sequence. CD spectroscopy indicated that the choice of template has an effect on the overall structure of the carboprotein, as the altro-based carboprotein was found to be more alpha-helical than the corresponding galacto- and gluco-carboproteins. However, an influence on stability could not be detected in the present experiments, as the three carboproteins gave similar free energy of foldings (deltaG(F)H2O) and melting points in chemical and thermal denaturation experiments.     

Separable states are more disordered globally than locally

A remarkable feature of quantum entanglement is that an entangled state of two parties, Alice ( A) and Bob ( B), may be more disordered locally than globally. That is, S(A)>S(A,B), where S(*) is the von Neumann entropy. It is known that satisfaction of this inequality implies that a state is nonseparable. In this paper we prove the stronger result that for separable states the vector of eigenvalues of the density matrix of system AB is majorized by the vector of eigenvalues of the density matrix of system A alone. This gives a strong sense in which a separable state is more disordered globally than locally and a new necessary condition for separability of bipartite states in arbitrary dimensions.     

Local vibrational modes of isolated hydrogen in germanium

Two distinct isolated hydrogen defects are observed in crystalline Ge by in situ infrared absorption spectroscopy. Implantation of protons into Ge at cryogenic temperatures gives rise to two intense absorption lines at 745 and 1794 cm(-1). The lines originate from distinct defects, each of which contains one H atom located on a <111> axis. The 1794-cm(-1) line is assigned to bond center H in the positive charge state, whereas the 745-cm(-1) line is ascribed to negatively charged H located on a <111> axis close to the tetrahedral site.