Highly versatile enantioselective conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters

Herein, we report efficient catalysts for the asymmetric copper-catalyzed conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters. MeMgBr adds to aromatic alpha,beta-unsaturated thioesters with excellent enantioselectivities and moderate to good yields using Josiphos/CuBr and Tol-BINAP/CuI complexes. The use of bulky Grignard reagents leads to unprecedented enantioselectivities in the 1,4-addition to a broad range of aromatic and aliphatic alpha,beta-unsaturated thioesters using Tol-BINAP/CuI. The highest enantioselectivities reported so far for the addition of Grignard reagents to crowded beta-substituted aliphatic substrates are achieved with Tol-BINAP/CuI.     

Ruthenium-manganese complexes for artificial photosynthesis: factors controlling intramolecular electron transfer and excited-state quenching reactions

Continuing our work toward a system mimicking the electron-transfer steps from manganese to P(680)(+) in photosystem II (PS II), we report a series of ruthenium(II)-manganese(II) complexes that display intramolecular electron transfer from manganese(II) to photooxidized ruthenium(III). The electron-transfer rate constant (k(ET)) values span a large range, 1 x 10(5)-2 x 10(7) s(-1), and we have investigated different factors that are responsible for the variation. The reorganization energies determined experimentally (lambda = 1.5-2.0 eV) are larger than expected for solvent reorganization in complexes of similar size in polar solvents (typically lambda approximately 1.0 eV). This result indicates that the inner reorganization energy is relatively large and, consequently, that at moderate driving force values manganese complexes are not fast donors. Both the type of manganese ligand and the link between the two metals are shown to be of great importance to the electron-transfer rate. In contrast, we show that the quenching of the excited state of the ruthenium(II) moiety by manganese(II) in this series of complexes mainly depends on the distance between the metals. However, by synthetically modifying the sensitizer so that the lowest metal-to-ligand charge transfer state was localized on the nonbridging ruthenium(II) ligands, we could reduce the quenching rate constant in one complex by a factor of 700 without changing the bridging ligand. Still, the manganese(II)-ruthenium(III) electron-transfer rate constant was not reduced. Consequently, the modification resulted in a complex with very favorable properties.     

Comparison of a modification of the ellman method to measure carbamate inhibition of acetylcholinesterase in plasma, erythrocytes and brain tissues in sprague dawley rats using two analytical systems

Inhibition of the enzyme acetylcholinesterase (AChE) using a carbamate compound was measured in 30 Crl: CD(R)BR Sprague Dawley rats. Erythrocyte, plasma, and brain tissues were analyzed using modifications of the Ellman technique(1) on two different clinical chemistry analyzers. Both EDTA and heparin anticoagulated whole blood were used for the erythrocyte and plasma tests. Results demonstrated similar inhibition of the enzyme in all three tissues between the control and dosed groups using the two technique modifications and instruments. Final inhibition of plasma and erythrocyte AChE for the control vs. treated groups (males and females combined) was 89.5% vs. 82% and 39% vs. 38% for the Technicon AutoAnalyzertrade mark vs. the Boehringer Mannheim Hitachitrade mark 704, respectively. Inhibition of the left and right brain segments for the control vs. treated groups (males and females combined) was 35% vs. 39% and 33.2% vs. 29% for the Technicon and the Hitachi, respectively. All inhibitions were significant at the 5% level using two tailed Dunnett's t-Test. Hemolysates prepared from EDTA whole blood packed cells gave more consistent results on the Hitachi 704.     

Construction of time-inhomogeneous Markov processes via evolution equations using pseudo-differential operators

For a pseudo-differential operator with symbol which is time-and space-dependent, elliptic and continuous negative definite,the corresponding evolution equation is solved. Further, itis shown that the solution defines a Markov process. In general,this will be a time- and spaceinhomogeneous jump process. Tosolve the evolution equation, we combine a fixed-point methodwith the symbolic calculus for negative definite symbols developedby Hoh. The properties of the fundamental solution which ensurethe existence of a corresponding Markov process are proved alongthe lines of Eidelman, Ivasyshen and Kochubei. However, insteadof hyper-singular integral representations, we use the pseudo-differentialoperator representation together with the positive maximum principleto obtain the required properties.     

Multiscale methods for the wave equation

We consider the wave equation in a medium with a rapidly varying speed of propagation. We construct a multiscale scheme based on the heterogeneous multiscale method, which can compute the correct coarse behavior of wave pulses traveling in the medium, at a computational cost essentially independent of the size of the small scale variations. This is verified by theoretical results and numerical examples. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure/Property Relationships for Polyamide 6 / Organoclay Nanocomposites in the Melt and in the Solid State

Commercial nanocomposites of polyamide 6 prepared by melt compounding with organoclays were characterized by complex viscosities and relaxation time spectra derived from storage and loss shear moduli measured in the melt state at 230°C, and by wide- and small-angle X-ray scattering, differential scanning calorimetry and stretching calorimetry in the solid state. In the melt state, the decrease of ∼ 25 % (compared to the pristine sample) in Newtonian viscosity at the lowest clay loading (2.5 %) suggested a lower equilibrium elasticity modulus of an entangled melt, as the small amounts of organoclay nanoparticles acted as specific “diluents” for the initial entanglement network. However, by increasing the clay loading this effect disappeared due to the importance of strong interactions at the nanoparticle/melt interface, leading to the formation of a fairly thick boundary interphase (BI) around the nanoparticles and ending up in the build-up of an “infinite cluster” of clay nanoparticles coated with BI at the highest (albeit still unusually low) clay loading (7.5 %). In the solid state, organoclay nanoparticles proved to induce the crystallographic α → γ transformation of PA6 , while the matrix crystallinity in nanocomposites remained essentially unchanged. In the range of elastic (reversible) behavior below the apparent yield strains ϵ* , the highest Young's moduli E and the lowest linear thermal expansion coefficients α_L were observed for dried nanocomposites, while the lowest E and the highest α_L corresponded to the moisturized, pristine PA6. The endothermal process of shape distortion of the lamellar crystals was assumed to precede the onset of the exothermal process of lamellar fragmentation in the range of inelastic (irreversible) behaviour of PA6 above ϵ* . The energy balance of the inelastic behaviour of nanocomposites was dominated by the endothermal process of lamellar shape distortion.     

Numerical methods for oscillatory solutions to hyperbolic problems

Difference approximations of hyperbolic partial differential equations with highly oscillatory coefficients and initial values are studied. Analysis of strong and weak convergence is carried out in the practically interesting case when the discretization step sizes are essentially independent of the oscillatory wave lengths. © 1993 John Wiley & Sons, Inc.