Palladium-catalyzed asymmetric addition of pronucleophiles to allenes

Simple additions are the most atom economic way to effect alkylations. The ability to effect the hydrocarbonation of allenes asymmetrically then becomes a highly efficient alkylation protocol. The first example of such a protocol involves the ability of a palladium(0) catalyst derived from palladium trifluoroacetate dimer and the bis-2-diphenylphosphinobenzamide of trans-1,2-diamininocyclohexane to catalyze additions to benzyloxyalkene. Various substituted Meldrum's acids including hydroxy Meldrum's acid react well in the presence of 1 mol % trifluoroacetic acid to give one regioisomer with ee's ranging from 82 to 99%. Switching to azlactones to access unusual quarternary amino acids requires somewhat more basic conditions. Thus, use of 2 mol % potassium alpha-butoxide and 20 mol % hippuric acid leads to a smooth reaction to produce a simple regiosomer. This nucleophile raises the question of facial selectivity with respect to both the nucleophile and the electrophile. Excellent diastereoselectivity (dr 13-20:1) and enantioselectivity (85-94% ee) are obtained. Thus, a new approach for asymmetric allylic alkylations of carbon pronucleophiles by simple additions provides a very efficient, more atom economic strategy for asymmetric C-C bond formation.     

Die Kristallstruktur von KPdMIVF7 (MIV = Zr,Hf)

The Crystal Structure of KPdM^IVF₇ (M^IV = Zr, Hf) Blue single crystals of KPdZrF₇ are obtained by heating the binary fluorides in sealed Pt-tubes under dry argon (solid state reaction, T ≈? 720°C, t ≈? 14 d). The compound crystallizes orthorhombically in the space group Pnna-D (Nr. 52); lattice parameters are a = 1 132.3(5) pm, b = 797.5(2) pm, c = 639.8(1) pm; Z = 4 (Four cycle diffractometer data, AED2). According to [F₄PdF_2/1ZrF₅] distortet [PdF₆]-octaedra are connected with pentagonal-bipyramidal [ZrF₇]-polyhedra via two bridging F^?, resulting in [PdZrF₁₁]-groups. These [PdZrF₁₁]-groups built up a threedimensional-network with K⁺ in its spacings. KPdHfF₇ crystallizes isotypically (a = 1 136.1(3) pm, b = 796.4(2) pm und c = 638.8(1) pm; four cycle diffractometer data, AED2).     

Comparison of data analysis parameters and MS/MS fragmentation techniques for quantitative proteome analysis using isobaric peptide termini labeling (IPTL)

Isobaric peptide termini labeling (IPTL) is a quantification method which permits relative quantification using quantification points distributed throughout the whole tandem mass spectrometry (MS/MS) spectrum. It is based on the complementary derivatization of peptide termini with different isotopes resulting in isobaric peptides. Here, we use our recently developed software package IsobariQ to investigate how processing and data analysis parameters can improve IPTL data. Deisotoping provided cleaner MS/MS spectra and improved protein identification and quantification. Denoising should be used with caution because it may remove highly regulated ion pairs. An outlier detection algorithm on the ratios within every individual MS/MS spectrum was beneficial in removing false-positive quantification points. MS/MS spectra using IPTL typically contain two peptide series with complementary labels resulting in lower Mascot ion scores than non-labeled equivalent peptides. To avoid this penalty, the two chemical modifications for IPTL were specified as variables including satellite neutral losses of tetradeuterium with positive loss for the heavy isotopes and negative loss for the light isotopes. Thus, the less dominant complementary ion series were not considered for the scoring, which improved the ion scores significantly. In addition, we showed that IPTL was suitable for fragmentation by electron transfer dissociation (ETD) and higher energy collisionally activated dissociation (HCD) besides the already reported collision-induced dissociation (CID). Notably, ETD and HCD data can be identified and quantified using IsobariQ. ETD outperformed CID and HCD only for charge states ≥4+ but yielded in total fewer protein identifications and quantifications. In contrast, the high-resolution information of HCD fragmented peptides provided most identification and quantification results using the same scan speed.     

A Convenient Synthesis of 3- and 3,4-Substituted 4,5-Dihydroisoxazole-5-Acetic Acids

The 4,5-dihydroisoxazole-5-acetic acids 4a-j were prepared from the ketoximes 1a-j, 2,2-dimethyl-5-methoxymethylene-1,3-dioxan-4,6-dione (2) and butyllithium in yields from 35 to 79%.     

Interaction of torsion and lateral bending in aircraft nose landing gear shimmy

In this paper we consider the onset of shimmy oscillations of an aircraft nose landing gear. To this end we develop and study a mathematical model with torsional and lateral bending modes that are coupled through a wheel-mounted elastic tyre. The geometric effects of a positive rake angle are fully incorporated into the resulting five-dimensional ordinary differential equation model. A bifurcation analysis in terms of the forward velocity and the vertical force on the gear reveals routes to different types of shimmy oscillations. In particular, we find regions of stable torsional and stable lateral shimmy oscillations, as well as transient quasiperiodic shimmy where both modes are excited.     

Control based bifurcation analysis for experiments

We introduce a method for tracking nonlinear oscillations and their bifurcations in nonlinear dynamical systems. Our method does not require a mathematical model of the dynamical system nor the ability to set its initial conditions. Instead it relies on feedback stabilizability, which makes the approach applicable in an experiment. This is demonstrated with a proof-of-concept computer experiment of the classical autonomous dry-friction oscillator, where we use a fixed time step simulation and include noise to mimic experimental limitations. For this system we track in one parameter a family of unstable nonlinear oscillations that forms the boundary between the basins of attraction of a stable equilibrium and a stable stick-slip oscillation. Furthermore, we track in two parameters the curves of Hopf bifurcation and grazing-sliding bifurcation that form the boundary of the bistability region. PACS 05.45-a, 02.30.Oz, 05.45.Gg Mathematics Subject Classification (2000) 37M20, 37G15, 37M05 The research of J.S. was supported by EPSRC grant GR/R72020/01, and that of B.K. by an EPSRC Advanced Research Fellowship.     

Motion analysis of a diaphragmless driver section for a narrow channel shock tube

We set up a diaphragmless driver section as the first step towards developing a shock tube at microscale which has high experimental efficiency, independent of tube dimensions or the ratio of driver and driven pressure. The experiment described in this paper is performed by using our diaphragmless driver section. We measured the operating time and the velocity of the fast opening valve. Additionally we have introduced and calculated the differential equation, by using the Runge–Kutta–Gill method, to understand the motion of the fast opening valve. We achieved good agreement between experimental and calculated results for the velocity. We can conclude that the diaphragmless driver section is highly suitable for a narrow channel shock tube.      

On the need of mode interpolation for data-driven Galerkin models of a transient flow around a sphere

We present a low-dimensional Galerkin model with state-dependent modes capturing linear and nonlinear dynamics. Departure point is a direct numerical simulation of the three-dimensional incompressible flow around a sphere at Reynolds numbers 400. This solution starts near the unstable steady Navier–Stokes solution and converges to a periodic limit cycle. The investigated Galerkin models are based on the dynamic mode decomposition (DMD) and derive the dynamical system from first principles, the Navier–Stokes equations. A DMD model with training data from the initial linear transient fails to predict the limit cycle. Conversely, a model from limit-cycle data underpredicts the initial growth rate roughly by a factor 5. Key enablers for uniform accuracy throughout the transient are a continuous mode interpolation between both oscillatory fluctuations and the addition of a shift mode. This interpolated model is shown to capture both the transient growth of the oscillation and the limit cycle.