Gas-phase stereoselective binding to Mn/salen catalysts

Gas-phase equilibrium measurements have been used to determine the stereoselectivity of binding the enantiomers of 1-phenylethanol to manganese/salen asymmetric epoxidation catalysts. There is significant selectivity in the gas-phase binding, and the results are compared to data from condensed-phase epoxidations. The study demonstrates the utility of a novel internal standard approach that allows for rapid, accurate measures of the stereoselectivity of gas-phase ligand binding. Moreover, the data suggest that gas-phase binding stereoselectivity could be a potential predictor of condensed-phase enantioselectivity.     

Convergence of an adaptive semi-Lagrangian scheme for the Vlasov-Poisson system

An adaptive semi-Lagrangian scheme for solving the Cauchy problem associated to the periodic 1+1-dimensional Vlasov-Poisson system in the two- dimensional phase space is proposed and analyzed. A key feature of our method is the accurate evolution of the adaptive mesh from one time step to the next one, based on a rigorous analysis of the local regularity and how it gets transported by the numerical flow. The accuracy of the scheme is monitored by a prescribed tolerance parameter ε which represents the local interpolation error at each time step, in the L ^∞ metric. The numerical solutions are proved to converge in L ^∞ towards the exact ones as ε and Δt tend to zero provided the initial data is Lipschitz and has a finite total curvature, or in other words, that it belongs to . The rate of convergence is , which should be compared to the results of Besse who recently established in (SIAM J Numer Anal 42(1):350–382, 2004) similar rates for a uniform semi-Lagrangian scheme, but requiring that the initial data are in . Several numerical tests illustrate the effectiveness of our approach for generating the optimal adaptive discretizations.     

Filling of a given boundary by p-gons and related problems

We consider here (p,s)-polycycles (3ps) i.e. plane graphs, such that all interior faces are p-gons, all interior vertices are s-valent and any vertex of the boundary (i.e. the exterior face) has valency within [2,s]. The boundary sequence of a (p,s)-polycycle P is the sequence b(P) enumerating, up to a cyclic shift or reversal, the consecutive valencies of vertices of the boundary. We show that the values p=3,4 are the only ones, such that the boundary sequence defines its (p,3)-filling (i.e. a (p,3)-polycycle with given boundary) uniquely.Also we give new results in the enumeration of maps M_n(p,q) (i.e. plane 3-valent maps with only p- and q-gonal faces, such that the q-gons are organized in an n-ring) and two of their generalizations.Both problems are similar (3-valent filling by p-gons of a boundary or of a ring of q-gons) and the same programs were used for both computations.     

Asymptotic results for bifurcations in pure bending of rubber blocks

The bifurcation of an incompressible neo-Hookean thick blockwith a ratio of thickness to length , subject to pure bending,is considered. The two incremental equilibrium equations correspondingto a nonlinear pre-buckling state of strain are reduced to afourth-order linear eigenproblem that displays a multiple turningpoint. It is found that for 0 < < , the block experiencesan Euler-type buckling instability which in the limit degeneratesinto a surface instability. Singular perturbation methods enableus to capture this transition, while direct numerical simulationscorroborate the analytical results.     

Design of phenotypic screens for bioactive chemicals and identification of their targets by genetic and proteomic approaches

Cell-based screening using phenotypic assays is a useful means of identifying bioactive chemicals for use as tools to elucidate complex cellular processes. However, the chemicals must display sufficient selectivity and their targets have to be identified. We describe how cell-based screening assays can be designed to maximize the likelihood of discovering selective compounds through the choice of positive readouts, low chemical concentrations and long incubation periods. Examining the potency, efficacy and activity range of chemicals can further help set apart those likely to act more specifically. Identifying the cellular targets of active chemicals can be especially demanding. Secondary screens and the cautious use of the candidate approach can help narrow down their mechanisms of action, but biased approaches may lead to the identification of secondary or even irrelevant targets. We discuss strategies for unbiased target identification by sampling potential targets at the genome-wide and proteome-wide levels.     

Carbon‐Centered Radical Addition and β‐Scission Reactions: Modeling of Activation Energies and Pre‐exponential Factors

A consistent set of group additive values ΔGAV° for 46 groups is derived, allowing the calculation of rate coefficients for hydrocarbon radical additions and β-scission reactions. A database of 51 rate coefficients based on CBS-QB3 calculations with corrections for hindered internal rotation was used as training set. The results of this computational method agree well with experimentally observed rate coefficients with a mean factor of deviation of 3, as benchmarked on a set of nine reactions. The temperature dependence on the resulting ΔGAV°s in the broad range of 300–1300 K is limited to ±4.5 kJ mol⁻¹ on activation energies and to ±0.4 on logA (A: pre-exponential factor) for 90 % of the groups. Validation of the ΔGAV°s was performed for a test set of 13 reactions. In the absence of severe steric hindrance and resonance effects in the transition state, the rate coefficients predicted by group additivity are within a factor of 3 of the CBS-QB3 ab initio rate coefficients for more than 90 % of the reactions in the test set. It can thus be expected that in most cases the GA method performs even better than standard DFT calculations for which a deviation factor of 10 is generally considered to be acceptable.