Biomimetic organocatalytic asymmetric synthesis of 2-substituted piperidine-type alkaloids and their analogues

Natural substances such as pelletierine and its analogues have been prepared in up to 97% ee and good yield by a protective-group-free, biomimetic approach. Usage of benzonitrile or acetonitrile as solvents effectively prevents product racemization.     

Beyond NICS: estimation of the magnetotropicity of inorganic unsaturated planar rings

A simple classical model of magnetic-field induced electron flow is used to evaluate the ring current strength for a few inorganic monocyclic compounds: B(3)H(3)N(3), B(3)H(3)O(3), P(6), N(6), Si(6)H(6), N, Al and H(6). It is shown that, for these neutral and charged systems, sustaining delocalized electron currents in the presence of a magnetic field B(ext) orthogonal to the σ(h) plane, the out-of-plane component of the nuclear magnetic shielding along the central axis is connected to the out-of-plane magnetizability by a simple equation, involving the radius of an average loop of current. A novel estimate of this effective radius is provided. Reliable ring current susceptibilities (that is, current strengths) can be evaluated by a simple relationship, using the out-of-plane components of nuclear shielding and magnetizability tensors. The accuracy of the current susceptibilities calculated by the classical model is established by comparison with corresponding ab initio estimates obtained by integrating the quantum mechanical current-density vector field. The out-of-plane components of nuclear shielding and magnetizability are both strongly biased by the molecular geometry. Their combined use to estimate the ring current susceptibility offers a quantifier of magnetotropicity more reliable than (i) the ξ(∥) out-of-plane component of magnetizability, (ii) the σ(∥)(CM) out-of-plane component of the magnetic shielding at the center of mass, widely reported as NICS(∥)(0) = -σ(∥)(CM). The inadequacy of these commonly adopted magnetotropicity measures is demonstrated by comparing a set of related molecules, C(6)H(6) and Si(6)H(6), N(6) and P(6).     

Purely linear response of the quantum Hall current to space-adiabatic perturbations

Letters in Mathematical Physics - We provide an algorithm that factorizes one-dimensional quantum walks on an arbitrary but fixed cell structure into a protocol of two basic operations: a fixed...     

An integer optimization approach for reverse engineering of gene regulatory networks

Gene regulatory networks are a common tool to describe the chemical interactions between genes in a living cell. This paper considers the Weighted Gene Regulatory Network (WGRN) problem, which consists in identifying a reduced set of interesting candidate regulatory elements which can explain the expression of all other genes. We provide an integer programming formulation based on a graph model and derive from it a branch-and-bound algorithm which exploits the Lagrangian relaxation of suitable constraints. This allows to determine lower bounds tighter than CPLEX on most benchmark instances, with the exception of the sparser ones. In order to determine feasible solutions for the problem, which appears to be a hard task for general-purpose solvers, we also develop and compare two metaheuristic approaches, namely a Tabu Search and a Variable Neighborhood Search algorithm. The experiments performed on both of them suggest that diversification is a key feature to solve the problem.     

Projective planes of Lenz�CBarlotti class V

We overview some recent results on projective planes of Lenz?CBarlotti class V.     

High-resolution inelastic x-ray scattering to study the high-frequency atomic dynamics of disordered systems

The use of momentum-resolved inelastic x-ray scattering with meV energy resolution to study the high-frequency atomic dynamics in disordered systems is here reviewed. The typical realization of this experiment is described together with some common models used to interpret the measured spectra and to extract parameters of interest for the investigation of disordered systems. With the help of some selected examples, the present status of the field is discussed. Particular attention is given to those results which are still open for discussion or controversial, and which will require further development of the technique to be fully solved. Such an instrumental development seems nowadays possible at the light of recently proposed schemes for advanced inelastic x-ray scattering spectrometers. To cite this article: G. Monaco, C. R. Physique 9 (2008).