Ylidaddukte der Penteltrichloride

Ylide Adducts of Pentele Trichlorides Ylides Ph₃PCR₂ form 1 : 1 adducts with PCl₃, AsCl₃ und SbCl₃. The addition of HCl to dichlorophosphanyl- und dichloroarsanyl ylides also leads to such adducts. In solution the PCl₃ adducts 2 are dissociated into ions. For the AsCl₃ adducts 3 b and 3 e of triphenylphosphonium ethylide and isopropylide X-ray analyses show distinctly different degrees of transition from a zwitterionic ψ-tbp to a cationic ψ-tetrahedral structure. The SbCl₃ adduct 4 b of the triphenylphosphonium ethylide on the other hand forms a rather asymmetric dimer and approaches a square-pyramidal geometry at the antimony atom. The 2 : 1 ylide adducts 11 with PCl₃ form in solution the dications (Ph₃PCR₂)₂PCl²⁺. The 2 : 3 adduct 15 of triphenylphosphonium methylide to AsCl₃ also has an ionic structure in the crystal. There are cations (Ph₃PCH₂)₂AsCl²⁺, which pairwise join with two AsCl₃ molecules to form doubly charged supracations in the presence of As₂Cl₈^2– as counterions.     

Niche-dependent development of functional neuronal networks from embryonic stem cell-derived neural populations

Background  

The present work was performed to investigate the ability of two different embryonic stem (ES) cell-derived neural precursor populations to generate functional neuronal networks in vitro. The first ES cell-derived neural precursor population was cultivated as free-floating neural aggregates which are known to form a developmental niche comprising different types of neural cells, including neural precursor cells (NPCs), progenitor cells and even further matured cells. This niche provides by itself a variety of different growth factors and extracellular matrix proteins that influence the proliferation and differentiation of neural precursor and progenitor cells. The second population was cultivated adherently in monolayer cultures to control most stringently the extracellular environment. This population comprises highly homogeneous NPCs which are supposed to represent an attractive way to provide well-defined neuronal progeny. However, the ability of these different ES cell-derived immature neural cell populations to generate functional neuronal networks has not been assessed so far.     

Simultaneous in situ monitoring of surface and gas species and surface properties by modulation excitation polarization-modulation infrared reflection-absorption spectroscopy: CO oxidation over Pt film

A method for in situ monitoring of surface and gas species utilizing separately the difference and sum reflectivity of two polarizations, normal and parallel to the surface, measured by polarization-modulation infrared reflection-absorption spectroscopy is presented. Surface and gas-phase spectra were separately but simultaneously obtained from the reflectivities. The technique is combined with modulation excitation spectroscopy to further enhance the sensitivity, and a small-volume cell was designed for this purpose. CO oxidation over a 40 nm Pt film on aluminum was investigated under moderate pressure (atmospheric pressure, 5% CO, and 5%-40% O2) at 373-433 K. The surface species involved in the oxidation process and the gas-phase species, both reactant (CO) and product (CO2), could be simultaneously monitored and analyzed quantitatively. In addition, the reflectivity change of the sample during the reaction was assigned to a near-surface bulk property change, that is, surface reconstruction to the oxide phase. Under an O2-rich atmosphere, two reactive phases, denoted as low- and high-activity phases, were identified. A large amount of atop CO was observed during the low-activity phase, while the adsorbed CO completely disappeared during the high-activity phase. The presence of an infrared-inactive CO2 precursor formed by the reaction between surface oxide and gaseous CO during the high-activity phase was inferred. The desorption of the CO2 precursor is facilitated under a CO-rich atmosphere, most likely, by surface reconstruction to metallic Pt and a competitive adsorption of CO on the surface.     

A measuring system for the fast simultaneous isotope ratio and elemental analysis of carbon, hydrogen, nitrogen and sulfur in food commodities and other biological material

The isotope ratio of each of the light elements preserves individual information on the origin and history of organic natural compounds. Therefore, a multi-element isotope ratio analysis is the most efficient means for the origin and authenticity assignment of food, and also for the solution of various problems in ecology, archaeology and criminology. Due to the extraordinary relative abundances of the elements hydrogen, carbon, nitrogen and sulfur in some biological material and to the need for individual sample preparations for H and S, their isotope ratio determination currently requires at least three independent procedures and approximately 1 h of work. We present here a system for the integrated elemental and isotope ratio analysis of all four elements in one sample within 20 min. The system consists of an elemental analyser coupled to an isotope ratio mass spectrometer with an inlet system for four reference gases (N(2), CO(2), H(2) and SO(2)). The combustion gases are separated by reversible adsorption and determined by a thermoconductivity detector; H(2)O is reduced to H(2). The analyser is able to combust samples with up to 100 mg of organic material, sufficient to analyse samples with even unusual elemental ratios, in one run. A comparison of the isotope ratios of samples of water, fruit juices, cheese and ethanol from wine, analysed by the four-element analyser and by classical methods and systems, respectively, yielded excellent agreements. The sensitivity of the device for the isotope ratio measurement of C and N corresponds to that of other systems. It is less by a factor of four for H and by a factor of two for S, and the error ranges are identical to those of other systems.     

Monitoring of liquid-phase organic reactions by photoelectron spectroscopy

There are strings attached: after linking the reacting groups to head groups of ionic liquids to drastically lower the vapour pressures of the reactants, ordinary liquid-phase organic reactions can be monitored by in situ X-ray photoelectron spectroscopy. This approach is demonstrated for the nucleophilic substitution of an alkyl amine and an alkyl chloride moiety, which are attached to the cation and anion of ionic liquids, respectively.     

Spatially-resolved potential measurement with ion crystals

We present a method to measure potentials over an extended region using one-dimensional ion crystals in a radio frequency (RF) ion trap. The equilibrium spacings of the ions within the crystal allow the calculation of the external forces acting at each point. From this the overall potential is computed, and even potentials due to specific trap features can be determined. The method can be used to probe potentials near proximal objects in real time, and can be generalised to higher dimensions.     

Toward an ion–photon quantum interface in an optical cavity

We demonstrate several building blocks for an ion–photon interface based on a trapped ⁴⁰Ca⁺ ion in an optical cavity. We identify a favorable experimental configuration and measure system parameters, including relative motion of the trapped ion and the resonator mode. A complete spectrum of cavity-assisted Raman transitions between the 4²S_1/2 and 3²D_5/2 manifolds is obtained. On two of these transitions, we generate orthogonally polarized cavity photons, and we demonstrate coherent manipulation of the corresponding pair of atomic states. Possible implementations of atom-photon entanglement and state mapping within the ion-cavity system are discussed.     

Kinetics of the sulfur oxidation on palladium: a combined in situ x-ray photoelectron spectroscopy and density-functional study

We studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (~0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO(4), with SO(2) and SO(3) being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO(2), SO(3), and eventually SO(4), also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From the experiments we determined the activation energy of the rate limiting step to be 85 ± 6 kJ mol(-1) by Arrhenius analysis, matching the calculated endothermicity of the SO formation.     

A Law of the Iterated Logarithm for Randomly Stopped Sums of Heavy Tailed Random Vectors

 Let be an i.i.d. sequence of -valued random vectors belonging to the generalized domain of semistable attraction of some nonnormal law. Assume further that is a sequence of positive integer valued random variables such that for some for some discrete positive random variable D, where we do not assume that and are independent. Let . Then various laws of the iterated logarithm for the norm of as well as the radial projection onto a unit vector θ are presented. (Received 31 January 2000; in revised form 5 April 2000)     

Optimal Control of One-Dimensional Partial Differential Algebraic Equations with Applications

We present an approach to compute optimal control functions in dynamic models based on one-dimensional partial differential algebraic equations (PDAE). By using the method of lines, the PDAE is transformed into a large system of usually stiff ordinary differential algebraic equations and integrated by standard methods. The resulting nonlinear programming problem is solved by the sequential quadratic programming code NLPQL. Optimal control functions are approximated by piecewise constant, piecewise linear or bang-bang functions. Three different types of cost functions can be formulated. The underlying model structure is quite flexible. We allow break points for model changes, disjoint integration areas with respect to spatial variable, arbitrary boundary and transition conditions, coupled ordinary and algebraic differential equations, algebraic equations in time and space variables, and dynamic constraints for control and state variables. The PDAE is discretized by difference formulae, polynomial approximations with arbitrary degrees, and by special update formulae in case of hyperbolic equations. Two application problems are outlined in detail. We present a model for optimal control of transdermal diffusion of drugs, where the diffusion speed is controlled by an electric field, and a model for the optimal control of the input feed of an acetylene reactor given in form of a distributed parameter system.