Dynamic kinetic resolution of atropisomeric amides

[reaction: see text] Using L-proline as catalyst in the asymmetric aldol reaction and a series of benzamides and naphthamides, we have accomplished a dynamic kinetic resolution that simultaneously establishes the stereochemistry of the atropisomeric amide's chiral axis and a stereogenic center. The enantioselectivities ranged from 82% to 95% and the diastereoselectivities from 2.1:1 to 7.0:1.     

Existence of Baryons,Baryon Spectrum and Mass Splitting in Strong Coupling Lattice QCD

We consider a functional integral formulation for one-flavor lattice Quantum Chromodynamics in d=2,3 space dimensions and imaginary time, and work in the regime of the small hopping parameter , and zero plaquette coupling. Following the standard construction, this model exhibits positivity which is used to obtain the underlying physical Hilbert space . Then, using a Feynman-Kac formalism, we write the correlation functions for the model as functional integrals over the space of Grassmannian (fermionic) fields for one quark specie and the SU(3) gauge fields. We determine the energy-momentum spectrum associated with gauge invariant local baryon (anti-baryon) fields which are composites of three quark (anti-quark) fields. With the associated correlation functions, we establish a Feynman-Kac formula, and a spectral representation for the Fourier transform of the two-point functions. This representation allows us to show that baryons and anti-baryons arise as tightly bound, bound states of three (anti-)quarks. Labelling the components of the baryon fields by s=3/2,1/2,-1/2,-3/2, we show that the baryon and anti-baryon mass spectrum only depends on |s|, and the associated masses are given by M_s= –3ln+r_s(), where r_s() is real analytic in , for each d=2,3. The mass splitting is M_3/2–M_1/2=18⁶, for d=2 and, if any, is at least of (⁷), for d=3. In the subspace _o generated by an odd number of fermions, the baryon and anti-baryon energy-momentum dispersion curves are isolated up to near the baryon-meson threshold –5ln (upper gap property), identical and are determined up to (⁵). The symmetries of coordinate reflections, spatial lattice rotations, parity and charge conjugation are established for the correlation functions, and are shown to be implemented on by unitary (anti-unitary, for time reversal) operators.     

Azimuthal anisotropy and correlations at large transverse momenta in p + p and Au + Au collisions at square root sNN=200 GeV

Results on high transverse momentum charged particle emission with respect to the reaction plane are presented for Au + Au collisions at square root s(NN)=200 GeV. Two- and four-particle correlations results are presented as well as a comparison of azimuthal correlations in Au + Au collisions to those in p + p at the same energy. The elliptic anisotropy v(2) is found to reach its maximum at p(t) approximately 3 GeV/c, then decrease slowly and remain significant up to p(t) approximately 7-10 GeV/c. Stronger suppression is found in the back-to-back high-p(t) particle correlations for particles emitted out of plane compared to those emitted in plane. The centrality dependence of v(2) at intermediate p(t) is compared to simple models based on jet quenching.     

An organometallic inhibitor for glycogen synthase kinase 3

Replacing natural products with kinetically inert metal complexes may lead to a new class of therapeutics in which a metal center plays the role of an innocent bystander, organizing the orientation of the organic ligands in the receptor space. As an example of this approach, a ruthenium complex is described that copies the binding mode of indolocarbazole protein kinase inhibitors and serves as a reversible, low-nanomolar inhibitor for glycogen synthase kinase 3 (GSK-3).     

Effect of the counterion on the rate of electron transfer in dendrimer films

The electrochemical behavior of a film composed of a redox-active dendrimer was studied as a function of the type of counterion available during its reduction and reoxidation. The rate of permeation/migration of counterions into the film appeared to be the bottleneck to electron transfer through the film. Because the dendrimer is rather hydrophobic, increasing the hydrophobicity of the counterion increased the rate and extent of electron hopping within the films.     

Reactions of arachno-6,8-C2B7H12- with electron deficient olefins: syntheses of cyano-substituted carboranes

The syntheses of new cyano-substituted derivatives of arachno-6,8-C(2)B(7)H(13) have been achieved through the addition reactions of the arachno-6,8-C(2)B(7)H(12)(-) (1-) anion with cyano-activated olefins. The reaction of PSH+1- with tetracyanoethylene (TCNE) yielded the unusual bridging compound PSH(+)endo-6-endo-7-[micro(2)-(C(CN)(2))(2)]-arachno-6,8-C(2)B(7)H(12)(-) (PSH+2-)) resulting from cycloaddition of the TCNE at the C6-B7 edge of the anion. Consistent with its hypho skeletal electron count, an X-ray crystallographic study and DFT/GIAO calculations confirm 2(-) has a more open structure than 1-. The reaction of 1- with acrylonitrile resulted in the formation of endo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(11)(-) (3-), which, upon acidification, afforded endo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(12) (3) in high yield. X-ray crystallographic and DFT/GIAO studies established that the cyanoethyl fragment in 3 is substituted at the endo-position of the C6 cage-carbon. Heating 3 in THF at 50 degrees C or in toluene at 110 degrees C resulted in the quantitative isomerization of the cyanoethyl-substituent from the endo- to the exo-position at C6 to yield exo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(12) (4). This is the first example of an endo to exo isomerization to be observed at a cage-carbon of a carborane. While heating 3 resulted in isomerization to 4, heating 3- in the presence of a small amount of 3 yielded the new ethylene-bridged 10-vertex tricarbaborane micro(6,9)-(CH(2)CH(2))-arachno-5,6,9-C(3)B(7)H(11) (5) resulting from reduction of the 3- pendant nitrile group, followed by deammination and carbon insertion.     

Angular dependence of the dipole-dipole interaction in a nearly one-dimensional sample of Rydberg atoms

Atoms in an ultracold highly excited sample are strongly coupled through the dipole-dipole interaction. In an effort to understand and manipulate the complicated interactions in this system we are investigating their dependence on the relative orientation of the dipoles. By focusing a 480 nm beam from a tunable dye laser into a magneto-optical trap, we produce a nearly one-dimensional sample of Rydberg atoms. The trap lies at the center of four conducting rods with which we can vary the magnitude and direction of the electric field at the trap, thus controlling the orientation of the dipoles with respect to the sample axis. We have measured the strength of the interaction for a variety of relative orientations.     

Proton transfer versus redox modulation in thiourea-phenanthrenequinone molecular and polymeric complexes

Phenanthrenequinone undergoes highly efficient proton transfer processes in the presence of a thiourea-functionalised polystyrene copolymer whereas interactions with a similar benzyl-thiourea monomer show strong redox modulation of the quinone without proton transfer.     

Centrality dependence of charged-hadron transverse-momentum spectra in d+Au collisions at sqrt[s(NN)]=200 GeV

We have measured transverse momentum distributions of charged hadrons produced in d+Au collisions at sqrt[s(NN)]=200 GeV. The spectra were obtained for transverse momenta 0.25相似文献