Novel stereocontrolled addition of allylmetal reagents to alpha-imino esters: efficient synthesis of chiral tetrahydroquinoline derivatives

To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives.     

Complexation behavior of a highly preorganized 7,7-diphenylnorbornane-derived macrocycle: towards the design of molecular clocks

The syntheses of two new cyclophane hosts, 4 and 6, are described. The main difference between them is the higher degree of preorganization of 4 as a consequence of the inclusion of the 7,7-diphenylnorbornane (DPN) subunit. The inner cavity of 4 adopts a belt-shaped structure, while 6 has a twisted geometry. In the solid state, the molecules of macrocycle 6 are stacked along an axis to form nanotubular structures. Compounds 4 and 6 form two of the strongest complexes between arene cyclophanes and Ag(+) reported up to date. The silver cation is located inside the cavity of the macrocycles. The stability of 4.Ag(+) is considerably higher than that of 6.Ag(+). The additional stabilization of 4.Ag(+) is attributed to higher preorganization of macrocycle 4. DNMR experiments as well as theoretical calculations carried out with 4.Ag(+) show evidence of Ag(+)-hopping between two different binding sites inside the macrocycle. This phenomenon could be the basis for the design of molecular clocks.     

The reproducible properties of correct forecasts

Each period, one outcome out of finitely many possibilities is observed. Each period, a forecaster announces some probability for the future outcomes based on the available data. An outsider wants to know if the forecaster has some knowledge of the data generating process. Let a test be an arbitrary function from sequences of forecasts and outcomes to {0,1}. When the test returns a 0 the test is said to reject the forecasts based on the outcome sequence. When the test resturns a 1 the test is said to not reject the forecasts based on the outcome sequence. Consider any test that does not reject the truth, i.e. it does not reject when the announced forecasts are the conditional probabilities of the data generating process. Based on Fans (1953) Minimax theorem, I show that it is possible to produce forecasts that will not be rejected on any sequence of outcomes. Journal of Economic Literature Classification Number:D83 LearningI thankfully acknowledge financial support from the National Science Foundation grant SES 0109650. I also thank a referee for useful comments. All errors are mine.     

Zeroes of complete polynomial vector fields

We prove that a complete polynomial vector field on has at most one zero, and analyze the possible cases of those with exactly one which is not of Poincaré-Dulac type. We also obtain the possible nonzero first jet singularities of the foliation at infinity and the nongenericity of completeness. Connections with the Jacobian Conjecture are established.

     

High yield production of long branched Au nanoparticles characterized by atomic resolution transmission electron microscopy

Long multi-branched gold nanoparticles have been synthesized in a very high yield through a facile synthesis combining two different capping agents. The stability of these materials with the time has been tested and their characterization have been performed by diverse advanced electron microscopy techniques, paying special attention to aberration corrected transmission electron microscopy in order to unambiguously analyze the surface structure of the branches and provide insights for the formation of stellated gold nanoparticles.     

catena-Poly­[[di­aqua(1,10-phen­anthroline-N,N′)­manganese(II)]-μ-(thiosulfato-O:S)] and bis(2,2′-bipyridyl-N,N′)(tetra­thionato-O,O′)manganese(II)

The structures of [Mn(S₂O₃)₂(C₁₂H₈N₂)(H₂O)₂] and [Mn(S₄O₆)(C₁₀H₈N₂)₂] are presented. The former consists of pairs of polymeric chains formed by manganese polyhedra bridged by bidentate thio­sulfate anions, which are in turn related to each other by a pseudo-twofold screw axis. The latter has crystallographic twofold symmetry and consists of monomers in which manganese displays its typical octahedral coordination provided by the bidentate bites of two bi­pyridine bases and a tetra­thionate anion, which is, to our knowledge, the first chelating tetra­thionate to be reported in the literature.     

Synthesis and characterization of new complexes of the type [Ru(CO)2Cl2 (2‐phenyl‐1,8‐naphthyridine‐kN) (2‐phenyl‐1,8‐naphthyridine‐kN′)]. Preliminary applications in homogeneous catalysis

Novel ruthenium (II) complexes were prepared containing 2‐phenyl‐1,8‐naphthyridine derivatives. The coordination modes of these ligands were modified by addition of coordinating solvents such as water into the ethanolic reaction media. Under these conditions 1,8‐naphthyridine (napy) moieties act as monodentade ligands forming unusual [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] complexes. The reaction was reproducible when different 2‐phenyl‐1,8‐naphthyridine derivatives were used. On the other hand, when dry ethanol was used as the solvent we obtained complexes with napy moieties acting as a chelating ligand. The structures proposed for these complexes were supported by NMR spectra, and the presence of two ligands in the [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] type complexes was confirmed using elemental analysis. All complexes were tested as catalysts in the hydroformylation of styrene showing moderate activity in N,N′‐dimethylformamide. Copyright © 2008 John Wiley & Sons, Ltd.     

A study of spectral element and discontinuous Galerkin methods for the Navier–Stokes equations in nonhydrostatic mesoscale atmospheric modeling: Equation sets and test cases

We present spectral element (SE) and discontinuous Galerkin (DG) solutions of the Euler and compressible Navier–Stokes (NS) equations for stratified fluid flow which are of importance in nonhydrostatic mesoscale atmospheric modeling. We study three different forms of the governing equations using seven test cases. Three test cases involve flow over mountains which require the implementation of non-reflecting boundary conditions, while one test requires viscous terms (density current). Including viscous stresses into finite difference, finite element, or spectral element models poses no additional challenges; however, including these terms to either finite volume or discontinuous Galerkin models requires the introduction of additional machinery because these methods were originally designed for first-order operators. We use the local discontinuous Galerkin method to overcome this obstacle. The seven test cases show that all of our models yield good results. The main conclusion is that equation set 1 (non-conservation form) does not perform as well as sets 2 and 3 (conservation forms). For the density current (viscous), the SE and DG models using set 3 (mass and total energy) give less dissipative results than the other equation sets; based on these results we recommend set 3 for the development of future multiscale research codes. In addition, the fact that set 3 conserves both mass and energy up to machine precision motives us to pursue this equation set for the development of future mesoscale models. For the bubble and mountain tests, the DG models performed better. Based on these results and due to its conservation properties we recommend the DG method. In the worst case scenario, the DG models are 50% slower than the non-conservative SE models. In the best case scenario, the DG models are just as efficient as the conservative SE models.     

A new approach for modelling the damped Helmholtz oscillator:applications to plasma physics and electronic circuits

In this paper,a new approach is devoted to find novel analytical and approximate solutions to the damped quadratic nonlinear Helmholtz equation(HE)in terms of the Weiersrtrass elliptic function.The exact solution for undamped HE(integrable case)and approximate/semi-analytical solution to the damped HE(non-integrable case)are given for any arbitrary initial conditions.As a special case,the necessary and sufficient condition for the integrability of the damped HE using an elementary approach is reported.In general,a new ansatz is suggested to find a semi-analytical solution to the non-integrable case in the form of Weierstrass elliptic function.In addition,the relation between the Weierstrass and Jacobian elliptic functions solutions to the integrable case will be derived in details.Also,we will make a comparison between the semi-analytical solution and the approximate numerical solutions via using Runge-Kutta fourth-order method,finite difference method,and homotopy perturbation method for the first-two approximations.Furthermore,the maximum distance errors between the approximate/semi-analytical solution and the approximate numerical solutions will be estimated.As real applications,the obtained solutions will be devoted to describe the characteristics behavior of the oscillations in RLC series circuits and in various plasma models such as electronegative complex plasma model.