Looking at Fokker-Planck dynamics with a noisy instrument

We consider the class of experiments which can be characterized by a Fokker-PIanck dynamics corresponding to the overdamped motion of a state point in a suitable stochastic potential. We assume that the general form of the potential is known (or can be guessed with reasonable accuracy), but that its parameters are to be determined experimentally by measurements made with a noisy instrument. This possible method for determining the potential parameters, which exploits the system's own internal stochastic motion in order to explore rapidly its available parameter space, is substantially more efficient than traditional methods involving time averages of single point measurements, and yet does not appear to have been previously considered. The method could be important when, for example, the experiment must be completed in a limited time owing either to the expense of the experimental materials or to the temporary stationarity of the preparation, situations which are commonly encountered in experimental biochemistry and biology.     

Alpha-sulfinyl carbanions as a new source of olefins

[reaction: see text] Secondary alpha-lithiosulfinyl carbanions react either intermolecularly, after transmetalation into an organocopper derivative in an S(N)2-type process with zinc carbenoid, or intramolecularly via higher-order zincate to give, through a tandem zinc homologation-beta-elimination reaction the corresponding alkenes. alpha,alpha-Disubstituted alkenes are only formed from tertiary alpha-lithiosulfinyl carbanions via the 1,2-metalate rearrangement.     

Electron-cluster interactions

Beam depletion spectroscopy has been used to measure absolute total inelastic electron-sodium cluster collision cross sections in the energy range fromE0.1 toE6 eV. The investigation focused on the closed shell clusters Na₈, Na₂₀, and Na₄₀. The measured cross sections show an increase for the lowest collision energies where electron attachment is the primary scattering channel. The electron attachment cross section can be understood in terms of Langevin scattering, connecting this measurement with the polarizability of the cluster. For energies above the dissociation energy the measured electron-cluster cross section is energy independent, thus defining an electron-cluster interaction range. This interaction range increases with the cluster size.     

The role of additional solvents in transition metal complex catalyzed asymmetric reductions in ionic liquid containing systems

When ionic liquids (ILs) are employed as solvents for transition metal complex (TMC) catalyzed reductions, a second solvent can be added to increase the efficiency of the catalytic cycle and the solubility of the reactant in the IL phase. Two industrially relevant asymmetric hydrogenations, the enantioselective reductions of methyl 2-acetamidoacrylate with Rh-EtDuPHOS and methyl acetoacetate with Ru-BINAP, were performed in different catalytic systems including 1-butyl-3-methylimidazolium hexafluorophosphate/ tetrafluoroborate as ILs. Product separation and TMC recycling was performed by extracting the product from the reaction mixture. This can be accomplished by cooling the system, by adding an excess of the second solvent or by adding a third solvent. A high solubility of the second solvent in the IL catalytic phase favors the reaction activity, but can induce leaching of the IL and TMC.     

The Newton Bracketing Method for Convex Minimization

An iterative method for the minimization of convex functions f :ⁿ , called a Newton Bracketing (NB) method, is presented. The NB method proceeds by using Newton iterations to improve upper and lower bounds on the minimum value. The NB method is valid for n = 1, and in some cases for n > 1 (sufficient conditions given here). The NB method is applied to large scale Fermat–Weber location problems.     

Dendritic effect in polymer-supported catalysis of the intramolecular Pauson-Khand reaction

A remarkable increase in catalytic activity and selectivity in the intramolecular Pauson-Khand reaction is observed for Co complexes, immobilised on second- and third-generation dendron-functionalized polystyrene, as compared with their analogues on non-dendronized support.     

Aqueous enantioselective hydrogenation of methyl 2-acetamidoacrylate with Rh-MeDuPHOS occluded in PDMS

A new chiral heterogeneous catalytic system obtained by occlusion of the Rh-MeDuPHOS complex in a polydimethylsiloxane film was tested in the asymmetric hydrogenation of methyl 2-acetamidoacrylate in aqueous medium.     

Noncontacting lateral transportation using gas squeeze film generated by flexural traveling waves--numerical analysis

This paper presents the theory describing the dynamical behavior of a noncontacting lateral transportation of planer objects by means of a gas squeeze film created by traveling flexural waves of a driving surface. An oscillating motion in the normal direction between two surfaces can generate a gas film with an average pressure higher than the surrounding. This load-carrying phenomenon arises from the fact that a viscous flow cannot be instantaneously squeezed; therefore, fast vibrations give rise to a cushioning effect. Equilibrium is established through a balance between viscous flow forces and compressibility forces. When the oscillatory motion between two surfaces creates traveling waves, lateral viscous forces are generated in addition to the normal levitation forces. These forces are produced as a result of nonuniform pressure gradients in the lateral direction between the surfaces. The combination of normal and lateral forces could be used for transporting objects without any direct contact with the driving surface. The numerical algorithm in this work couples the squeeze film phenomenon, which is represented by means of finite difference equations, to model a variant of the Reynolds equation, together with the equations describing the dynamics of the floating object. Numerical simulations are presented and investigated to highlight noteworthy topics.