Enantiodivergent Chemoenzymatic Dynamic Kinetic Resolution: Conversion of Racemic Propargyl Alcohols into Both Enantiomers

Natural lipases typically recognize enantiomers of alcohols based on the size differences of substituents near the carbinol moiety and selectively react with the R enantiomers of secondary alcohols. Therefore, lipase-catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols produces only R enantiomers. We report herein a method for obtaining S enantiomers by DKR of secondary 3-(trialkylsilyl)propargyl alcohols by using a well-known R-selective Pseudomonas fluorescens lipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. We have already reported R-selective DKR of the corresponding propargyl alcohols without substituents on the ethynyl terminal carbon, and the presence of an easily removable silyl group has enabled us to produce both enantiomers of propargyl alcohols in high chemical yields and with high enantiomeric excess. In addition, immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the DKR.     

Structural optimization of an asymmetric automotive brake disc with cooling channels to avoid squeal

Brake squeal is still a major issue in the automotive industry due to comfort complaints of passengers and resulting high warranty costs. Many measures to avoid squeal have been discussed in the engineering community reaching from purely passive measures like the increase of damping, e.g. by the application of shims, to the active or semiactive suppression of squeal. While active measures can be effective but are elaborate and therefore more expensive, passive measure are less complex in most cases. This leads to the necessity to develop passive, economic and robust measures to avoid squeal. Asymmetry of the brake rotor has been proposed to achieve this goal and the resulting split of all double eigenfrequencies of the brake rotor has lately been shown to stabilize the system.     

Synthesis and Characterization of Oxazaborinin Phosphonate for Blue OLED Emitter Applications

A blue-light emitting material based on a boron complex containing heteroaromatic phosphonate ligand is synthesized and characterized. The Phospho-Fries rearrangement is used in the synthesis route of the ligand as a convenient method of introducing phosphonate groups into phenols. Structural, thermal and photophysical properties of the resulting oxazaborinin phosphonate compound have been characterized. DFT geometry optimizations were studied as well as the spatial position and symmetry of the HOMO and LUMO. Good thermal stability up to 250 °C enables vacuum deposition methods next to solution processing. Combining the work function with the optical band gap from UV-Vis measurements shows that band alignment is possible with standard contact materials. Photoluminescence reveals an emission peak at 428 nm, which is suitable for a blue light-emitter.     

Parareal for index two differential algebraic equations

Numerical Algorithms - This article proposes modifications of the Parareal algorithm for its application to higher index differential algebraic equations (DAEs). It is based on the idea of applying...     

Hydrogen-Bond Structure and Dynamics of TADDOL Asymmetric Organocatalysts Correlate with Catalytic Activity

The catalytic efficiency of diol-based organocatalysts has been shown to strongly depend on the diols molecular structure including hydrogen-bonding, yet, the underlying molecular-level origins have remained elusive. Herein a study on the inter- and intramolecular hydrogen-bonding of two isomeric diol-based catalysts (TADDOLs) in solution is presented: 1-Naphthyl substituted TADDOL (1nTADDOL), which exhibits high catalytic efficiency, and 2-naphthyl substituted TADDOL (2nTADDOL), which is a poor catalyst. Using nuclear magnetic resonance and infrared spectroscopy, comparable hydrogen-bond strengths for both TADDOLs in solution were found, however, significantly slower bonding dynamics for 1nTADDOL. In aromatic solvents, 1nTADDOL forms less, but longer-lived, intermolecular OH⋅⋅⋅π bonds to solvent molecules, as compared to 2nTADDOL. Thus, rather than previously suggested differences in intermolecular hydrogen-bonding strengths, the results suggest that the hydrogen-bonding kinetics and entropies differ for both TADDOLs, which also explains their vastly different catalytic activities.     

Analytical calculation of in-plane response of plates with concentrated masses to impact and application to pyroshock simulation

In aerospace missions pyroshocks occur due to controlled explosions of ordnance devices enabling the functionality of space modules. These shocks result from deployment mechanisms or opening solar sails and can cause failures of electronic devices and structures. Thus, essential components for assuring the reliability of modules are pyroshock tests for the completion of which strict requirements by the aerospace administrations have to be met. One of them is the definition of a specific acceleration signal and, based on this, the Shock Response Spectrum (SRS) for each part.So far, there is rather empirical than analytical knowledge about producing desired SRS with mechanical impacts and its characteristics due to the variation of input parameters. In this paper a widespread testing procedure for far-field pyroshocks is discussed which is realized by the in-plane impact of a hammer pendulum on a plate including the test specimen. The mechanical model consists of the contact between a rigid sphere and a free deformable rectangular plate with attached masses including subsequent propagation and reflection of longitudinal waves. In order to allow for a prediction of the acceleration field and the corresponding SRS due to the impact the problem is solved semi-analytically by using Hertzian contact theory, the Galerkin-procedure and numerical integration in time domain. The in-plane problem has, to the best of the authors' knowledge, not yet been treated in the literature in the way presented.The results calculated are compared with experimental data showing very good coincidence and allowing for a fast prediction of far-field pyroshock tests due to the impact excitation by a hammer pendulum. Hence, the framework of this paper is an enrichment for the current state of the art considering analytical pyroshock simulation. By better understanding the effect of pyroshocks to one and two dimensional structures a reduction of costs as well as durations for testing procedures seems promising.     

Shallow-underground accelerator sites for nuclear astrophysics: Is the background low enough?

In order to reliably estimate the rate of a charged particle induced nuclear reaction in a non-explosive astrophysical scenario, its cross-section must be measured far below the Coulomb barrier. However, at the corresponding energies the cross-section values are very low, so that the experimental counting rate is dominated by cosmic-ray induced background, even if a suitable anticoincidence shield is applied. This problem can be overcome by performing an accelerator-based experiment in a deep underground site, as has been done with great success at the LUNA 0.4MV accelerator in Gran Sasso, Italy. Several underground accelerators with higher beam energy are in the planning phase worldwide. All of them are shielded by over 1000m of rock, a depth at which cosmic-ray effects are negligible for the purposes of nuclear astrophysics experiments. It is shown here that a combined approach, using a shallow-underground laboratory below 47m of rock and an active shield to veto surviving muons in simple detectors, results in a background level that is not far from that of deep underground sites. Data have been obtained using two ??traveling?? ??-detectors. They have been transported both shallow underground, to the Dresden Felsenkeller in Germany, and deep underground, to the Gran Sasso laboratory in Italy. As shallow-underground facilities are more easily accessible than deep-underground ones, the present finding holds the promise of greatly accelerated progress in the field of cross-section measurements for nuclear astrophysics.     

Using the phase plane and the computer for the study of systems dynamics

Because of their graphics capabilities, it is possible to use personal computers to analyse the behaviour of dynamical systems. We therefore require a way to introduce pedagogically both this technique and the important aspects of the study of non‐linear systems. This paper considers first the formal points of the phase plane method, and then presents three relevant examples: (a) second order linear systems; (b) the Van der Pol oscillator; and (c) the forced pendulum. In each case programs in Turbo‐Pascal are given for plotting the trajectories.