Properties of water in the interfacial region of a polyelectrolyte bilayer adsorbed onto a substrate studied by computer simulations

We study the static and dynamic properties of water near a poly(styrene sulfonate)/poly(diallyldimethylammonium) (PSS/PDADMA) bilayer adsorbed onto a substrate by atomistic molecular dynamics simulations. Qualitative changes in the dynamics of water in the proximity of the adsorbed bilayer are observed - such as in the lateral diffusion, residence time and hydrogen-bonding lifetime - as compared with water in the presence of the bare substrate. Static properties of water are similarly influenced, and a high polarization of water molecules is found to be present surprisingly far from the adsorbed bilayer.     

Synthesis of enantiopure 1,4-dioxanes, morpholines, and piperazines from the reaction of chiral 1,2-diols, amino alcohols, and diamines with vinyl selenones

The reactions of readily available vinyl selenones with enantiopure 1,2-diols, N-protected-1,2-aminoalcohols, and diamines gave substituted enantiopure 1,4-dioxanes, morpholines, and piperazines, respectively, in good to excellent yields. The same procedure was extended to the synthesis of thiomorpholine, benzodiazepine, and benzoxazepine. The reactions proceeded in one pot, in the presence of base, through a simple and novel application of the Michael-initiated, ring-closure (MIRC) reactions. The formed heterocycles constitute a framework that is observed in a large number of pharmaceutical compounds.     

Where is an object before you look at it?

According to the standard interpretation of quantum mechanics (QM), no meaning can be assigned to the statement that a particle has a precise value of any one of the variables describing its physical propertes before having interacted with a suitable measuring instrument. On the other hand, it is well known that QM tends to classical statistical mechanics (CSM) when a suitable classical limit is performed. One may ask therefore how is it that in this limit, the statement, meaningless in QM, that a given variable has always a precise value independently of having been measured, gradually becomes meaningful. In other words, one may ask how can it be that QM, which is a theory describing the intrinsically probabilistic properties of a quantum object, becomes a statistical theory describing a probabilistic knowledge of intrinsically well determined properties of classical objects.In the present paper we try to answer to this question and show that an inconsistency arises between the conventional interpretation of CSM which presupposes objectively existing Newtonian trajectories, and the standard interpretation of QM. We conclude that the latter needs revisiting unnless we wish to adopt a strictly subjective conception of the world around us, implying that macroscopic objects as well are not localized anywhere before we look at them.     

Pointwise gradient estimates in exterior domains

We consider a class of elliptic operators with unbounded coefficients in a smooth exterior domain Ω and we prove that the Cauchy-Neumann problem associated with admits, for any bounded and continuous initial datum, a unique bounded classical solution. We also provide pointwise gradient estimates for such a solution. Received: 5 July 2005; Revised: 20 December 2005     

Large eddy simulation of turbulent flows via domain decomposition techniques. Part 2: applications

The present paper discusses the application of large eddy simulation to incompressible turbulent flows in complex geometries. Algorithmic developments concerning the flow solver were provided in the companion paper (Int. J. Numer. Meth. Fluids, 2003; submitted), which addressed the development and validation of a multi‐domain kernel suitable for the integration of the elliptic partial differential equations arising from the fractional step procedure applied to the incompressible Navier–Stokes equations. Numerical results for several test problems are compared to reference experimental and numerical data to demonstrate the potential of the method. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrodynamical Modeling of Charge Carrier Transport in Semiconductors

Enhanced functional integration in modern electron devices requires an accurate modeling of energy transport in semiconductors in order to describe high-field phenomena such as hot electron propagation, impact ionization and heat generation in the bulk material. The standard drift-diffusion models cannot cope with high-field phenomena because they do not comprise energy as a dynamical variable. Furthermore for many applications in optoelectronics one needs to describe the transient interaction of electromagnetic radiation with carriers in complex semiconductor materials and since the characteristic times are of order of the electron momentum or energy flux relaxation times, some higher moments of the distribution function must be necessarily involved. Therefore these phenomena cannot be described within the framework of the drift-diffusion equations (which are valid only in the quasi-stationary limit). Therefore generalizations of the drift-diffusion equations have been sought which would incorporate energy as a dynamical variable and also would not be restricted to quasi-stationary situations. These models are loosely speaking called hydrodynamical models. One of the earliest hydrodynamical models currently used in applications was originally put forward by Blotekjaer [1] and subsequently investigated by Baccarani and Wordeman [2] and by other authors [3]. Eventually other models have also been investigated, some including also non-parabolic effects [4–6, 8–20]. Most of the implemented hydrodynamical models suffer from serious theoretical drawbacks due to the ad hoc treatment of the closure problem (lacking a physically convincing motivation) and the modeling of the production terms (usually assumed to be of the relaxation type and this, as we shall see, leads to serious inconsistencies with the Onsager reciprocity relations). In these lectures we present a general overview of the theory underlying hydrodynamical models. In particular we investigate in depth both the closure problem and the modeling of the production terms and present a recently introduced approach based on the maximum entropy principle (physically set in the framework of extended thermodynamics [21, 22]). The considerations and the results reported in the paper are exclusively concerned with silicon.     

Tightening of active site interactions en route to the transition state revealed by single-atom substitution in the guanosine-binding site of the Tetrahymena group I ribozyme

Protein enzymes establish intricate networks of interactions to bind and position substrates and catalytic groups within active sites, enabling stabilization of the chemical transition state. Crystal structures of several RNA enzymes also suggest extensive interaction networks, despite RNA's structural limitations, but there is little information on the functional and the energetic properties of these inferred networks. We used double mutant cycles and presteady-state kinetic analyses to probe the putative interaction between the exocyclic amino group of the guanosine nucleophile and the N7 atom of residue G264 of the Tetrahymena group I ribozyme. As expected, the results supported the presence of this interaction, but remarkably, the energetic penalty for introducing a CH group at the 7-position of residue G264 accumulates as the reaction proceeds toward the chemical transition state to a total of 6.2 kcal/mol. Functional tests of neighboring interactions revealed that the presence of the CH group compromises multiple contacts within the interaction network that encompass the reactive elements, apparently forcing the nucleophile to bind and attack from an altered, suboptimal orientation. The energetic consequences of this indirect disruption of neighboring interactions as the reaction proceeds demonstrate that linkage between binding interactions and catalysis hinges critically on the precise structural integrity of a network of interacting groups.     

CuI complexes with N,N',S,S' scorpionate ligands: evidence for dimer-monomer equilibria

The heteroscorpionate N, N', S, S' donor ligands 4-methoxy-3,5-dimethyl-2-(3-(methylthio)-1-(3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)propyl)pyridine (L(a)) and 4-methoxy-3,5-dimethyl-2-(2-(methylthio)-1-(3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)ethyl)pyridine (L(b)) were prepared. The Cu(I) complexes [Cu(L(a))]2(BF4)2 (a2(BF4)2) and [Cu(L(b))]2(BF4)2 (b2(BF4)2) were synthesized and characterized by X-ray crystallography. Both compounds exhibit a dinuclear structure, presenting each Cu(I) center in a distorted N, N', S, S' tetrahedral environment. On the basis of nuclear magnetic resonance (NMR) and ESI-mass data, the presence of a mononuclear complex in equilibrium with the dimer was hypothesized for both complexes. The dimerization constants of the processes, 2a(+) = a2(2+) and 2b(+) = b2(2+) , were obtained by (1)H NMR dilution experiments (fast-exchange regime) in CD 3CN: log K(a2(2+)) = 3.55(6) and log K(b2(2+)) = 3.23(5) at 300 K. Thermodynamic parameters were determined by a van't Hoff analysis (280-310 K temperature range): DeltaH(0)(a2(2+)) = -12(1) kJ mol (-1), DeltaH(0)(b2(2+)) = -10(1) kJ mol(-1), DeltaS(0)(a2(2+)) = +27(4) kJ mol (-1), and DeltaS(0)(b2(2+)) = +28(4) kJ mol (-1). Pulsed gradient spin-echo (PGSE) NMR experiments provided the weighted-average hydrodynamic volume (VH) of the species present in CD 3CN solution at different copper concentrations (CCu). Nonlinear interpolation of VH as a function of C Cu for a dimer-monomer equilibrium led to the hydrodynamic volumes of both monomers (VH(0)(M)) and dimers (VH(0)(D)): VH(0)(a(+)) = 620(40) A(3), VH(0)(b(+)) = 550(10) A(3), VH(0)(a2(2+)) = 950(20) A(3), and VH(0)(b2(2+)) = 900(10) A(3). Cyclic voltammetry experiments performed in CH3CN and CH2Cl2 showed a quasi-reversible to irreversible behavior of the Cu(I)/Cu(II) redox couple for both complexes.     

Six-dimensional potential energy surface for H2 at Ru(0001)

The six-dimensional (6D) potential energy surface (PES) for the H(2) molecule interacting with a clean Ru(0001) surface has been computed accurately for the first time. Density functional theory (DFT) and a pseudopotential based periodic plane-wave approach have been used to calculate the electronic interactions between the molecule and the surface. Two different generalized gradient approximation (GGA) exchange-correlation functionals, PW91 and RPBE, have been adopted. Based on the DFT/GGA calculated potential energies, an analytical 6D PES has been constructed using the corrugation reducing procedure. A very accurate representation of the DFT/GGA data has been achieved, with an average error in the interpolation of about 3 meV and a maximum error not larger than about 30 meV. The top site is found to be the most reactive site for both functionals used, but PW91 predicts a higher reactivity than RPBE, with lower-energy and earlier-located dissociation barriers. The energetic corrugation displayed by the RPBE PES is larger than the PW91 PES while the geometric corrugation is smaller. The differences between the two PESs increase as the distance of the molecular center of mass to the surface decreases. A direct comparison with experimental investigations on H(2)/Ru(0001) could shed light on the suitability of these XC potentials often used in DFT calculations.     

Selenium Promoted Stereospecific One-Pot Conversion Of Cinnamyl Derivatives Into Oxazoleses. A Simple Synthetic Route To Racemic Taxol Side Chain

A regiospecific and stereospecific conversion of cinnamyl methyl ether and cinnamyl acetate into the corresponding oxazolines can be easily effected by reaction with diphenyl diselenide and ammonium persulfate, in benzonitrile in the presence of acetic acid.