Analysis of the non-periodic oscillations of a self-excited friction-damped system with closely spaced modes

Nonlinear Dynamics - It is widely known that dry friction damping can bound the self-excited vibrations induced by negative damping. The vibrations typically take the form of (periodic) limit cycle...     

On the biological properties of alkynyl phosphine gold(i) complexes

Golden times for metal-based drugs? Alkynyl triphenylphosphine gold(I) complexes display interesting biological properties and show high potential for future drug development. They are strong inhibitors of the enzyme thioredoxin reductase, trigger antiproliferative effects in tumor cells, and influence tumor cell metabolism, mitochondrial respiration, and angiogenesis in zebrafish embryos.     

Characterising and optimising impulsive molecular alignment in mixed gas samples

Laser induced impulsive molecular alignment has been fully characterized in linear molecules by matching numerical simulations and experimental data of the corresponding rotational wavepacket in the frequency domain. A rigorous procedure for an accurate matching between simulation and experimental data is presented for the first time, making this a versatile technique for experiments where the molecular axis distribution is not directly accessible. Seeding small molecules in Ar as a carrier gas has then been employed to assist cooling and we systematically retrieve the molecule's rotational temperature and alignment distribution for different mixing ratios. For a total backing pressure of 2 bar it was found that seeding 10% N(2) in Ar results in the best cooling. Compared to pure N(2) the rotational temperature was reduced from 24 ± 2 K down to 9 ± 2 K. This leads to an improvement of the peak alignment distribution from = 0.60 to = 0.71. For the same mixing ratio CO(2) was cooled from 34 ± 3 K to 9 ± 1 K improving the alignment distribution from 0.48 to 0.64. In O(2) a cooling from 58 ± 2 K to 37 ± 4 K was observed, corresponding to an alignment distribution improvement from 0.49 to 0.58. The results demonstrate the wide applicability of the characterisation procedure and of seeded supersonic beams to optimise impulsive alignment of small molecules.     

On 1,3-phosphaazaallenes and their diverse reactivity

1,3-Phosphaazaallenes are heteroallenes of the type RP C NR′ and little is known about their reactivity. In here we describe the straightforward synthesis of ArPCNR (Ar = Mes*, 2,4,6-tBu-C₆H₂; ^MesTer, 2.6-(2,4,6-Me₃C₆H₂)–C₆H₃; ^DipTer, 2.6-(2,6-iPr₂C₆H₂)–C₆H₃; R = tBu; Xyl, 2,6-Me₂C₆H₃) starting from phospha-Wittig reagents ArPPMe₃ and isonitriles CNR. It is further shown that ArPCNtBu are thermally labile with respect to the loss of iso-butene and it is shown that the cyanophosphines ArP(H)CN are synthetically feasible and form the corresponding phosphanitrilium borates with B(C₆F₅)₃, whereas deprotonation of ^DipTerP(H)CN was shown to give an isolable cyanidophosphide. Lastly, the reactivity of ArPCNR towards Pier''s borane was investigated, showing hydroboration of the C N bond in Mes*PCNtBu to give a hetero-butadiene, while with ^DipTerPCNXyl the formation of the Lewis acid–base adduct with a B–P linkage was observed.

The combination of phospha-Wittig reagents with isonitriles affords 1,3-phosphaazaallenes and their diverse reactivity has been studied in detail.     

Synthesis of novel symmetrical, single-chain, diacetylene-modified bolaamphiphiles with different alkyl chain lengths

Abstract  

General syntheses of novel symmetrical, single-chain, diacetylene-modified bolaphospholipids have been carried out in five steps. For the ω-alkynols, which have an important role as key intermediates, three different synthetic approaches were comprehensively investigated. For the final synthesis it is suggested that (1) alkylation of lithium (trimethylsilyl)acetylide with tetrahydropyranyl-protected ω-bromoalcohols, followed by (2) cleavage of the trimethylsilyl moiety and the tetrahydropyranyl protecting group, and (3) copper(II)-catalyzed Eglinton coupling is the best strategy for obtaining diacetylene-modified alkane-1,ω-diols, because higher yields were obtained while avoiding the formation of by-products. Moreover, conversion of the diols into bipolar phospholipids was achieved by bis-phosphorylation with β-bromoethylphosphoric acid dichloride and subsequent quaternization with trimethylamine or dimethylamine. Finally, spectral data are presented for novel single-chain, diacetylene-modified bolaphospholipids with promising potential as starting molecules in the formation of polymerizable and, thus, thermostable nanofibers.     

Structural Effects of Cu/Zn Substitution in the Malachite–Rosasite System

Synthetic zincian malachite samples (Cu_1–xZn_x)₂(OH)₂CO₃ with x = 0, 0.1, 0.2 and 0.3 were characterized by powder X‐ray diffraction and optical spectroscopy. The XRD patterns of the samples up to x = 0.2 indicate single phase materials with an approximately linear dependence of the refined lattice parameters on the zinc content. In contrast, the sample with a nominal zinc content x = 0.3 shows the formation of a small amount of aurichalcite (Zn,Cu)₅(OH)₆(CO₃)₂ as an additional phase. Based on the lattice parameter variations, the zinc content of the zincian malachite component in this sample is estimated to be x ≈? 0.27, which seems to represent the maximum possible substitution in zincian malachite under the synthesis conditions applied. The results are discussed in relation to preparation of Cu/ZnO catalysts and the crystal structures of the minerals malachite and rosasite. One striking difference between these two structurally closely related phases is the orientation of the Jahn–Teller elongated axes of the CuO₆ octahedra in the unit cell, which seems to be correlated with the placement of the monoclinic β angle. The structural and chemical relationship between these crystallographically distinct phases is discussed using a hypothetical intermediate Zn₂(OH)₂CO₃ phase of higher orthorhombic symmetry. In addition to the crystallographic analysis, optical spectroscopy proves to be a useful tool for estimation of the Cu:Zn ratio in (Cu_1–xZn_x)₂(OH)₂CO₃ samples.     

Packing chained items in aligned bins with applications to container transshipment and project scheduling

Bin packing problems are at the core of many well-known combinatorial optimization problems and several practical applications alike. In this work we introduce a novel variant of an abstract bin packing problem which is subject to a chaining constraint among items. The problem stems from an application of container handling in rail freight terminals, but is also of relevance in other fields, such as project scheduling. The paper provides a structural analysis which establishes computational complexity of several problem versions and develops (pseudo-)polynomial algorithms for specific subproblems. We further propose and evaluate simple and fast heuristics for optimization versions of the problem.     

A Flow Cytometry-Based Ultrahigh-Throughput Screening Method for Directed Evolution of Oxidases

Oxidases are of interest to chemical and pharmaceutical industries because they catalyze highly selective oxidations. However, oxidases found in nature often need to be re-engineered for synthetic applications. Herein, we developed a versatile and robust flow cytometry-based screening platform “FlOxi” for directed oxidase evolution. FlOxi utilizes hydrogen peroxide produced by oxidases expressed in E. coli to oxidize Fe²⁺ to Fe³⁺ (Fenton reaction). Fe³⁺ mediates the immobilization of a His₆-tagged eGFP (eGFP^His) on the E. coli cell surface, ensuring the identification of beneficial oxidase variants by flow cytometry. FlOxi was validated with two oxidases—a galactose oxidase (GalOx) and a D-amino acid oxidase (D-AAO)—yielding a GalOx variant (T521A) with a 4.4-fold lower K_m value and a D-AAO variant (L86M/G14/A48/T205) with a 4.2-fold higher k_cat than their wildtypes. Thus, FlOxi can be used for the evolution of hydrogen peroxide-producing oxidases and applied for non-fluorescent substrates.     

Study of the biomechanical behaviour of structurally stable/unstable motion segments of the sheep spine

The effects of damage of intervertebral discs on their biomechanical behaviour and the factors favouring the progression of instability are studied. Healthy and damaged movement segments are analyzed experimentally and numerically. The aim is to represent and predict the effects of tissue damage and changes in the spine by comparison with healthy segments. Since the intervertebral disc acts as a mechanical damper, relaxation tests are performed in addition to pressure experiments. The experiments are carried out in a bioreactor with tempered nutrient solution. A cultivation period in the bioreactor allows detecting cell viability, solute diffusion rates and gene expression of the discs. Numerically, the nonlinear, viscoelastic, anisotropic and diffusion-dependent behaviour of the intervertebral disc is modelled with the FE-program Abaqus, using a modular material law as a UMAT subroutine. With the measurement results, the relevant parameters can be determined so that the mechanical behaviour of intervertebral discs can be simulated. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)