N,N-dichloro-2-nitrobenzenesulfonamide as the electrophilic nitrogen source for direct diamination of enones

N,N-dichloro-o-nitrobenzenesulfonamide (2-NsNCl2) was found to be an effective electrophilic nitrogen source for the direct diamination of alpha,beta-unsaturated ketones without the use of any metal catalysts. The reaction is very convenient to carry out without the protection of inert gases. Molecular sieves (4 A) and temperature were found to play key roles in controlling the formations of 3-trichloromethyl and dichloromethyl imidazoline products (16 examples). The 2-Ns-protection group of the resulting diamine products can be easily cleaved under mild Fukuyama's conditions. A new mechanism hypothesis of [2+3] cyclization and N-chlorination has been proposed to explain the product structures, particularly their regio- and stereochemistry.     

Dynamic combinatorial libraries of metalloporphyrins: templated amplification of disulfide-linked oligomers

Disulfide-linked cyclic porphyrin oligomers from dimer to tetramer can be selected and amplified virtually quantitatively from a dynamic combinatorial library using bis-thiol substituted zinc(II) porphyrin units with appropriate amine donor templates.     

Homomorphic Feller Cocycles on a C*-Algebra

When a Fock-adapted Feller cocycle on a C*-algebra is regular,completely positive and contractive, it possesses a stochasticgenerator that is necessarily completely bounded. Necessaryand sufficient conditions are given, in the form of a sequenceof identities, for a completely bounded map to generate a weaklymultiplicative cocycle. These are derived from a product formulafor iterated quantum stochastic integrals. Under two alternativeassumptions, one of which covers all previously considered cases,the first identity in the sequence is shown to imply the rest.     

Experimental evidence for a light and broad scalar resonance in D(+) --> pi(-)pi(+)pi(+) decay

From a sample of 1172 +/- 61 D(+)-->pi(-)pi(+)pi(+) decays, we find gamma(D(+)-->pi(-)pi(+)pi(+))/gamma(D(+)-->K-pi(+)pi(+)) = 0.0311 +/- 0.0018(+0.0016)(-0.0026). Using a coherent amplitude analysis to fit the Dalitz plot of these decays, we find strong evidence that a scalar resonance of mass 478(+24)(-23) +/- 17 MeV/c(2) and width 324(+42)(-40) +/- 21 MeV/c(2) accounts for approximately half of all decays.     

NMR-Based amide hydrogen-deuterium exchange measurements for complex membrane proteins: development and critical evaluation

A method for measuring site-specific amide hydrogen-deuterium exchange rates for membrane proteins in bilayers is reported and evaluated. This method represents an adaptation and extension of the approach of Dempsey and co-workers (Biophys. J. 70, 1777-1788 (1996)) and is based on reconstituting (15)N-labeled membrane proteins into phospholipid bilayers, followed by lyophilization and rehydration with D(2)O or H(2)O (control). Following incubation for a time t under hydrated conditions, samples are again lyophilized and then solubilized in an organic solvent system, where (1)H-(15)N HSQC spectra are recorded. Comparison of spectra from D(2)O-exposed samples to spectra from control samples yields the extent of the H-D exchange which occurred in the bilayers during time t. Measurements are site specific if specific (15)N labeling is used. The first part of this paper deals with the search for a suitable solvent system in which to solubilize complex membrane proteins in an amide "exchange-trapped" form for NMR quantitation of amide peak intensities. The second portion of the paper documents application of the overall procedure to measuring site-specific amide exchange rates in diacylglycerol kinase, a representative integral membrane protein. Both the potential usefulness and the significant limitations of the new method are documented.     

200GeV AuAu碰撞中前快度区的微分椭圆流

Identified particle elliptic flow results are presented for the Au+Au reaction at s_NN=200GeV as a function of transverse momentum and pseudorapidity. Data at pseudorapidities η≈0,1, and 3.4 were obtained using the two BRAHMS spectrometers. Differential v₂ (η,p_t) values for a given particle type are found to be essentially constant over the covered pseudorapidity range, in contrast to the integral v₂ values which have previously been observed to decrease at forward rapidities. A softening of the particle spectra at forward angles is found to account for at least part of the integral v₂ falloff. The data are found to be consistent with existing constituent quark scaling systematics.     

Thermal degradation and flame retardance in copolymers of methyl methacrylate with diethyl(methacryloyloxymethyl)phosphonate

Methyl methacrylate (MMA) has been free radically copolymerized, both in bulk and in solution, with diethyl(methacryloyloxymethyl)phosphonate (DEMMP), to give polymers which are significantly flame retarded when compared with PMMA, as indicated by the results of limiting oxygen index (LOI) measurements, UL 94 tests, and the results of cone calorimetric experiments. The physical and mechanical properties of the copolymers are similar to those of PMMA, except that the bulk copolymers are slightly crosslinked, and are better than those of PMMA flame retarded to a similar extent by some phosphate and phosphonate additives. Examination of the some of the gaseous products of pyrolysis and combustion, and of chars produced on burning, show that flame retardation occurs in the copolymers by both a condensed-phase and a vapour-phase mechanism. The condensed-phase mechanism is shown to involve generation of phosphorus acid species followed by reaction of these with MMA units giving rise to methacrylic acid units. The methacrylic acid units subsequently form anhydride links, which probably impede depolymerization of the remaining MMA sequences, resulting in evolution of less MMA (the major fuel when MMA-based polymers burn). By undergoing decarboxylation, leading to interchain cyclisation and, eventually, to aromaticisation, the anhydride units are probably also the principal precursors to char.