Discussion on appropriate material parameters for a porous media model of the IVD

The determination of the theoretically introduced material parameters is always a big issue, especially in computational biomechanics. In this context it is difficult to obtain the appropriate intervertebral disc (IVD) specimens within 24 h post decease and to perform reliable experiments on them, respectively. A complex test setup is needed for most of the cases and the measured results are very ‘patient specific’. On the other hand, the parameters obtained from literature are often also not reliable, because they are widespread, the experimental setup is not clearly described or was deficient. Moreover, as soft tissues generally exhibit a coupled dissipative behaviour, it is often not possible to measure these effects independently. Hence, the parameters have to be identified by inverse computations, i. e., axial compression, bending or torsion of a whole motion segment. The goal of this contribution is to proceed from an extended biphasic model and a set of suitable material parameters obtained from literature, in order to find the influence of certain parameters on a numerical compression-bending experiment of a L4-L5 motion segment. Finally, a comment on how the respective parameters should be determined is given. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Recent progress and future challenges in the supramolecular polymerization of metal-containing monomers

The self-assembly of discrete molecular entities into functional nanomaterials has become a major research area in the past decades. The library of investigated compounds has diversified significantly, while the field as a whole has matured. The incorporation of metal ions in the molecular design of the (supra-)molecular building blocks greatly expands the potential applications, while also offering a promising approach to control molecular recognition and attractive and/or repulsive intermolecular binding events. Hence, supramolecular polymerization of metal-containing monomers has emerged as a major research focus in the field. In this perspective article, we highlight recent significant advances in supramolecular polymerization of metal-containing monomers and discuss their implications for future research. Additionally, we also outline some major challenges that metallosupramolecular chemists (will) have to face to produce metallosupramolecular polymers (MSPs) with advanced applications and functionalities.

In this perspective article, we highlight recent significant advances in the self-assembly of metal-containing monomers and discuss their implications for future research.     

Correction: Expanding medicinal chemistry into 3D space: metallofragments as 3D scaffolds for fragment-based drug discovery

Correction for ‘Expanding medicinal chemistry into 3D space: metallofragments as 3D scaffolds for fragment-based drug discovery’ by Christine N. Morrison et al., Chem. Sci., 2020, 11, 1216–1225, https://doi.org/10.1039/C9SC05586J.

The authors regret that in the original article, inhibitory values reported for some metallofragments were incorrect. Unfortunately, DMSO stock solutions of reportedly active ferrocene-based metallofragments were found to decompose in the presence of light, which resulted in inaccurate inhibition values. The authors maintain that the core conclusions of the paper are accurate and the utility of three-dimensional metal complexes for fragment-based drug discovery has merit.In the original article, ‘class A’ metallofragments are comprised of ferrocene derivatives (Fig. 1). Some of these ferrocene fragments (specifically those containing carbonyl groups) are reported as broadly inhibiting several protein targets. It was noted in our original report that the ferrocene scaffold was likely promiscuous due to its lipophilicity and potential redox activity, but that it might still serve as a useful metallofragment for fragment-based drug discovery (FBDD) campaigns. However, re-evaluation of these compounds against the influenza endonuclease (PA_N) failed to reproduce our original inhibition results for the class A metallofragments using freshly prepared stocks, indicating a problem with the materials used in the original study.Open in a separate windowFig. 1Chemical structures of class A metallofragments.Several compounds from class A were originally reported as having near complete (100%) inhibition against PA_N endonuclease at an inhibitor concentration of 200 μM (​and2).2). However, when re-evaluated under identical conditions, using freshly prepared DMSO stock solutions, inhibition was only observed with one fragment of this class (A22, Fig. 1), with the previously reported highly active fragments (A4, A7–A21,

Probing fuel-specific reaction intermediates from laminar premixed flames fueled by two C5 ketones and model interpretations

The flame chemistry was explored for two C₅ ketones with distinct structural features, cyclopentanone (CPO) and diethyl ketone (DEK). Quantitative information for numerous species, including some reactive intermediates, was probed from fuel-rich (?= 1.5) laminar premixed flames fueled by the ketones with a photoionization molecular-beam mass spectrometer (PI-MBMS). Furthermore, a new kinetic model was proposed aimed at interpreting the high-temperature combustion chemistry for both ketones, which could satisfactorily predict the current flame speciation measurements. Experimental observations in combination with modeling analyses were used to reveal the similarities and differences between the compositions of the species pools of the two flames, with emphasis on the effects of the carbonyl functionality on pollutants formations. Besides some primary species which preserve fuel-specific features produced from initial steps of fuel consumptions, basic C₁C₄ intermediates also differ much between the two flames. More abundant intermediates were observed in the CPO flame because the cyclic fuel structure enables ring-opening processes followed by formations of C₃ and C₄ hydrocarbons which cannot be easily produced from the two isolated ethyl moieties in DEK under flame conditions. The consumptions of C₃C₄ hydrocarbons in the CPO flame further lead to larger C₅C₆ species which were under the detection limit in the DEK flame. In both flames, the tightly bonded carbonyl groups in the fuels tend to be preserved, leading to carbon monoxide through α-scissions of fuel-related acyl radicals. The carbonyl moieties in most detected C₁C₃ aldehydes and ketones form through oxidations of hydrocarbon species rather than directly originating from the fuels.     

HBr or not HBr? That is the question: crystal structure of 6‐hydroxy‐1,4‐diazepane‐1,4‐diium dibromide redetermined

Liu et al. [Chin. J. Struct. Chem. (1996). 15 , 371–373] reported the structure of 6‐hydroxy‐1,4‐diazepane di(hydrogen bromide), C₅H₁₂N₂O·2HBr, which was interpreted in terms of neutral diazepane and HBr molecules. We found, however, ample evidence that the formation of an organic salt, consisting of a diammonium cation and two bromide anions, is more plausible. This interpretation is also in agreement with thermogravimetric analysis and with the observed solution behaviour. The crystal structure of 6‐hydroxy‐1,4‐diazepane‐1,4‐diium dibromide, C₅H₁₄N₂O²⁺·2Br^?, measured at 142 K, crystallized in the orthorhombic space group P2₁2₁2₁. The structure displays O—H…Br and N—H…Br hydrogen bonding. Contact distances are given. A search in the Cambridge Structural Database for the singly‐bonded H—Br moiety revealed a total of 69 structures. The question, whether these structures really include HBr as neutral molecules or rather Br^? anions and a protonated substrate such as an amine, is addressed.     

QCMS2 as a new method for providing insight into peptide fragmentation: The influence of the side‐chain and inter–side‐chain interactions

The identification of peptides and proteins from tandem mass spectra is a difficult task and multiple tools have been developed to aid this identification. We present a new method called quantum chemical mass spectrometry for materials science (QCMS²), which is based on quantum chemical calculations of bond orders, reaction, and transition‐state energies at the DFT/B3LYP/6‐311+G* level of theory. The method was used to describe the fragmentation pathways of five X‐His‐Ser tripeptides with X = Asn, Asp, Glu, Ser, and Trp, thereby focusing on the influence of the side chain and inter–side‐chain interactions on the fragmentation. The main features in the mass spectra of the five tripeptides were correctly reproduced, and a number of fragments were assigned to fragmentations involving the side chain and the influence of inter–side‐chain interactions. Product ion spectra were recorded to evaluate the capabilities and limitations of QCMS² and a number of conventional tools.     

On two-scale convergence and related sequential compactness topics

A general concept of two-scale convergence is introduced and two-scale compactness theorems are stated and proved for some classes of sequences of bounded functions in L ²(Ω) involving no periodicity assumptions. Further, the relation to the classical notion of compensated compactness and the recent concepts of two-scale compensated compactness and unfolding is discussed and a defect measure for two-scale convergence is introduced.