Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

Mathematical Modeling, Control, Computer Simulation and Laboratory Experiments of a Spatial Servopneumatic Parallel Robot

In this paper, the special construction of a parallel robot, called spatial servopneumatic multi-axis test facility, will be discussed. The investigations include the following aspects: (i) the laboratory set-up of the robot, (ii) various results obtained in laboratory experiments, taking into account quite different control algorithms and command-input signals, (iii) a comparison of the laboratory experiments with the computer simulations of Part I of this paper, and ({vi}) a quality check of the results compared with the cost of the different controller realizations. The results of both the computer simulations and the laboratory experiments show: (i) The dynamic behavior of the parallel structure can be tremendously improved by using sophisticated nonlinear control algorithms. (ii) This improvement has to be paid by a drastically increased amount of work for deriving the model equations and control algorithms, and by augmented hardware cost of the sensing elements and controller electronics. (iii) Carefully developed model equations and identified model parameters provide theoretical models of the complex parallel structure that are very close to reality. This enables the design engineer to systematically investigate constructive alternatives of the design parameters, sensor and actuator concepts, and control strategies of the MAP prior to their hardware realization.This work has been supported by the German Science Foundation (DFG) under Contract No. Ha 1666/6-3.     

Expected Reflection Distance in G(r, 1, n) after a Fixed Number of Reflections

Extending to r > 1 a formula of the authors, we compute the expected reflection distance of a product of t random reflections in the complex reflection group G(r, 1, n). The result relies on an explicit decomposition of the reflection distance function into irreducible G(r, 1, n)-characters and on the eigenvalues of certain adjacency matrices.Received December 8, 2003     

Laser systems specialized for laser spectroscopy at storage rings

Laser spectroscopy at storage rings often suffers from a limited resolution due to Doppler-broadened resonances. Broadening is caused by the velocity spread of the ions stored in the beam. In the following, the present status of our work on laser systems specialized on the specific needs of laser spectroscopy at storage rings is reported. Two pulsed laser systems were developed. One is a dye laser whose spectral bandwidth can be switched by inserting different Littrow-prisms into the resonator. An increase in bandwidth up to a factor of 45 was achieved. This laser was used for fast qualitative scans and high resolution measurements. The other laser system is a Nd : YAG laser pumped optical parametric oscillator. It is a tunable laser system covering the spectral range from 410 to 4000 nm. Furthermore, a continuous wave laser with a frequency shifted feedback cavity is described. It shows broadband emission with an adjustable bandwidth of up to 4.5 GHz. This laser can be advantageous for laser cooling of ion beams. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Interaction of Shocks with Dispersive Waves II. Incompressible-Integrable Limit

This is the second in a two-part series of articles in which we analyze a system similar in structure to the well-known Zakharov equations from weak plasma turbulence theory, but with a nonlinear conservation equation allowing finite time shock formation. In this article we analyze the incompressible limit in which the shock speed is large compared to the underlying group velocity of the dispersive wave (a situation typically encountered in applications). After presenting some exact solutions of the full system, a multiscale perturbation method is used to resolve several basic wave interactions. The analysis breaks down into two categories: the nonlinear limit and the linear limit, corresponding to the form of the equations when the group velocity to shock speed ratio, denoted by ε, is zero. The former case is an integrable limit in which the model reduces to the cubic nonlinear Schrödinger equation governing the dispersive wave envelope. We focus on the interaction of a “fast” shock wave and a single hump soliton. In the latter case, the ε=0 problem reduces to the linear Schrödinger equation, and the focus is on a fast shock interacting with a dispersive wave whose amplitude is cusped and exponentially decaying. To motivate the time scales and structure of the shock-dispersive wave interactions at lowest orders, we first analyze a simpler system of ordinary differential equations structurally similar to the original system. Then we return to the fully coupled partial differential equations and develop a multiscale asymptotic method to derive the effective leading-order shock equations and the leading-order modulation equations governing the phase and amplitude of the dispersive wave envelope. The leading-order interaction equations admit a fairly complete analysis based on characteristic methods. Conditions are derived in which: (a) the shock passes through the soliton, (b) the shock is completely blocked by the soliton, or (c) the shock reverses direction. In the linear limit, a phenomenon is described in which the dispersive wave induces the formation of a second, transient shock front in the rapidly moving hyperbolic wave. In all cases, we can characterize the long-time dynamics of the shock. The influence of the shock on the dispersive wave is manifested, to leading order, in the generalized frequency of the dispersive wave: the fast-time part of the frequency is the shock wave itself. Hence, the frequency undergoes a sudden jump across the shock layer.In the last section, a sequence of numerical experiments depicting some of the interesting interactions predicted by the analysis is performed on the leading-order shock equations.     

From monomeric to polymeric ferroelectric liquid crystals A comparative study of ferroelectric properties

Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization P_s. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer.     

On cellularization for simplicial presheaves and motivic homotopy

We construct cellular homotopy theories for categories of simplicial presheaves on small Grothendieck sites and discuss applications to the motivic homotopy category of Morel and Voevodsky.     

Synthesis and applications of chiral bis-THF in asymmetric synthesis

The synthesis of enantiopure bis-THF is described, starting from d-mannitol. Bis-THF is used as chiral ligand for organolithium reagents in four different reactions. The enantioselectivity provided by this ligand is moderate, and the asymmetric induction is in line with the expected model.