Allyl strontium compounds: synthesis, molecular structure and properties

The synthesis and attempted isolation of neutral bis(allyl)strontium [Sr(C(3)H(5))(2)] (1) resulted in the isolation of potassium tris(allyl)strontiate K[Sr(C(3)H(5))(3)] (2). In situ generated 1 shows a pronounced Br?nsted basicity, inducing polymerisation of THF. Ate complex 2 crystallises as [K(THF)(2){Sr(C(3)H(5))(3)}(THF)](∞) (2·(THF)(3)). The salt-like solid state structure of 2·(THF)(3) comprises a two-dimensional network of (μ(2)-η(3):η(3)-C(3)H(5))(-) bridged potassium and strontium centres. Synthesis of allyl complexes 1 and 2 utilised SrI(2), [Sr(TMDS)(2)] (3) (TMDS = tetramethyldisilazanide), and [Sr(HMDS)(2)] (HMDS = hexamethyldisilazanide) as strontium precursors. The solid state structure of previously reported [Sr(TMDS)(2)] (3) was established by X-ray single crystal analysis as a dissymmetric dimer of [Sr(2)(TMDS)(4)(THF)(3)] (3·(THF)(3)) with multiple Si-HSr agostic interactions. The presence of ether ligands (THF, 18-crown-6) influenced the Si-HSr resonances in the NMR spectra of the amido complex 3.     

Selective proper orthogonal decomposition model reduction for forming simulations

Robot-based incremental sheet metal forming is a cost-effective and flexible method for prototype and low batch size production. The simulation of such processes is very challenging and elaborate from the computational point of view. To reduce the computational effort model reduction techniques such as proper orthogonal decomposition (POD) can be applied. But the reduction of highly non-linear models in solid mechanics for example forming simulation still leads to problems of efficiency and accuracy. Therefore, the aim of this paper is to present an alternative way to use POD for forming processes. The presented selective POD (SPOD) method is used to split the model into two domains depending on the degree of plastic strain. Only the domain with approximately linear elastic behavior will be reduced by using POD. Utilizing the SPOD method for the example of forming a horizontal flute reduces the computational time up to around 30 per cent. High accuracy with approximation errors smaller than one per mill is achieved. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application and evaluation of hyper- and hypoelastic-based plasticity models in the FE simulation of metal forming processes

Metal forming processes are usually accompanied by large plastic strains and rotations of the material elements which emphasizes the need for reliable finite strain elastoplasticity models in corresponding FE simulations. In this work, two specific finite strain hyper- and hypoelastic-based plasticity models with combined nonlinear isotropic and kinematic hardening are presented and compared in numerical FE simulations. Although both models led to remarkably different results in a shear-dominated single element deformation test, the structural simulation of a standard deep drawing process delivered nearly congruent results which suggests that both models are equally well-suited for modeling metals in common forming processes. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Predicting the onset of delamination in layered fiber-reinforced composites

In this paper, composite structures are considered which consist of several layers of carbon fiber reinforced plastics (CFRP). For such layered composite structures, delamination constitutes one of the major failure modes and hence predicting its initiation is essential for their design. Evaluating stress-strength relation based onset criteria requires an accurate representation of the through-the-thickness stress distribution, which can be particularly delicate in the case of shell-like structures. Thus, in this paper, a solid-shell finite element is utilized, which allows for incorporating a fully three-dimensional material model, still being suited for application to thin structures. Moreover, locking phenomena are cured by using both the EAS and the ANS concept, and numerical efficiency is ensured through reduced integration. The proposed anisotropic material model accounts for the material's micro-structure by using the concept of structural tensors. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Protochlorophyllide a: A Comprehensive Photophysical Picture

The photochemistry of protochlorophyllide a, a precursor in the biosynthesis of chlorophyll and substrate of the light regulated enzyme protochlorophyllide oxidoreductase, is investigated by pump‐probe spectroscopy. Upon excitation into the lowest lying Q‐band the light induced changes are recorded over a wide range of probe wavelengths in the visible and near‐IR region between 500 and 1000 nm. Following excitation, an initial ultrafast 450 fs process is observed related to the motion out of the Franck‐Condon region on the excited state surface; thus directly unraveling previous suggestions based on time‐resolved fluorescence measurements (ChemPhysChem 2006 , 7, 1727–1733). Furthermore, the data reveals a previously concealed photointermediate, whose formation on a nanosecond timescale matches the overall fluorescence decay and is assigned to a triplet state. The implications of this finding with respect to the photochemistry of NADPH:protochlorophyllide oxidoreductase (POR) are discussed.     

Focus on Fourier transform ion cyclotron resonance mass spectrometry

Editorial

Focus on Fourier transform ion cyclotron resonance mass spectrometry