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801.
Elisa Biasin Tim B. van Driel Gianluca Levi Mads G. Laursen Asmus O. Dohn Asbjørn Moltke Peter Vester Frederik B. K. Hansen Kasper S. Kjaer Tobias Harlang Robert Hartsock Morten Christensen Kelly J. Gaffney Niels E. Henriksen Klaus B. Møller Kristoffer Haldrup Martin M. Nielsen 《Journal of synchrotron radiation》2018,25(2):306-315
Time‐resolved X‐ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X‐ray free‐electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X‐ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time‐resolved X‐ray scattering experiment. This method is applied on time‐resolved X‐ray scattering patterns measured upon photoexcitation of a solvated di‐platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute, i.e. the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function. 相似文献
802.
Dr. Frederik Peschke Dr. Andrea Taladriz-Sender Dr. Matthew J. Andrews Prof. Allan J. B. Watson Prof. Glenn A. Burley 《Angewandte Chemie (International ed. in English)》2023,62(50):e202313063
Traditional approaches to bio-orthogonal reaction discovery have focused on developing reagent pairs that react with each other faster than they are metabolically degraded. Glutathione (GSH) is typically responsible for the deactivation of most bio-orthogonal reagents. Here we demonstrate that GSH promotes a Cu-catalysed (3+2) cycloaddition reaction between an ynamine and an azide. We show that GSH acts as a redox modulator to control the Cu oxidation state in these cycloadditions. Rate enhancement of this reaction is specific for ynamine substrates and is tuneable by the Cu:GSH ratio. This unique GSH-mediated reactivity gradient is then utilised in the dual sequential bio-orthogonal labelling of peptides and oligonucleotides via two distinct chemoselective (3+2) cycloadditions. 相似文献
803.
804.
Dr. Riccardo Conti Dr. Anna Widera Dr. Georgina Müller Csilla Fekete Debora Thöny Frederik Eiler Prof. Zoltán Benkő Prof. Hansjörg Grützmacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202202563
Addition of the P−H bond in bis(mesitoyl)phosphine, HP(COMes)2 (BAPH), to a wide variety of activated carbon–carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R−P(COMes)2, under very mild conditions in excellent yields after only a short time. All phosphines RP(COMes)2 can subsequently be oxidized to the corresponding bis(acyl)phosphane oxides, RPO(COMes)2, a substance class belonging to the most potent photoinitiators for radical polymerizations known to date. Thus, a simple and highly atom economic method has been found that allows the preparation of a broad range of photoinitiators adapted to their specific field of application even on a large scale. 相似文献
805.
806.
Dr. Xavier Deraet Dr. Jan Turek Prof. Mercedes Alonso Prof. Frederik Tielens Prof. Bert M. Weckhuysen Prof. Monica Calatayud Prof. Frank De Proft 《Chemphyschem》2023,24(6):e202200785
The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect-free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between −3.11 and −3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s-d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd−O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase-supported d-metal atoms. The values obtained from this regression model show, within a 95 % probability interval, a correlation of 84 % with the explicitly calculated CO adsorption energies. 相似文献
807.
Anna-Maria Tsirigoni Melis Goktas Zeynep Atris Angelo Valleriani Ana Vila Verde Kerstin G. Blank 《Macromolecular bioscience》2023,23(5):2200563
Coiled coils (CCs) are key building blocks of biogenic materials and determine their mechanical response to large deformations. Of particular interest is the observation that CC-based materials display a force-induced transition from α-helices to mechanically stronger β-sheets (αβT). Steered molecular dynamics simulations predict that this αβT requires a minimum, pulling speed-dependent CC length. Here, de novo designed CCs with a length between four to seven heptads are utilized to probe if the transition found in natural CCs can be mimicked with synthetic sequences. Using single-molecule force spectroscopy and molecular dynamics simulations, these CCs are mechanically loaded in shear geometry and their rupture forces and structural responses to the applied load are determined. Simulations at the highest pulling speed (0.01 nm ns−1) show the appearance of β-sheet structures for the five- and six-heptad CCs and a concomitant increase in mechanical strength. The αβT is less probable at a lower pulling speed of 0.001 nm ns−1 and is not observed in force spectroscopy experiments. For CCs loaded in shear geometry, the formation of β-sheets competes with interchain sliding. β-sheet formation is only possible in higher-order CC assemblies or in tensile-loading geometries where chain sliding and dissociation are prohibited. 相似文献
808.
The numerical analysis of ductile damage and failure in engineering materials is often based on the micromechanical model of Gurson [1]. Numerical studies in the context of the finite‐element method demonstrate that, as with other such types of local damage models, the numerical simulation of the initiation and propagation of damage zones is strongly mesh‐dependent and thus unreliable. The numerical problems concern the global load‐displacement response as well as the onset, size and orientation of damage zones. From a mathematical point of view, this problem is caused by the loss of ellipticity of the set of partial di.erential equations determining the (rate of) deformation field. One possible way to overcome these problems with and shortcomings of the local modelling is the application of so‐called non‐local damage models. In particular, these are based on the introduction of a gradient type evolution equation of the damage variable regarding the spatial distribution of damage. In this work, we investigate the (material) stability behaviour of local Gurson‐based damage modelling and a gradient‐extension of this modelling at large deformation in order to be able to model the width and other physical aspects of the localization of the damage and failure process in metallic materials. 相似文献
809.
Frederik Rummel Frerk Wehmeyer Dr. Matthias Vogt Prof. Dr. Robert Langer 《欧洲无机化学杂志》2023,26(28):e202300313
The thioether-group-containing SNS-type pincer complex [({EtSCH2CH2}2NH)RuCl(H)(PPh3)] ( 2 ) exists in three different diastereomers ( 2 a – c ). The molecular structures obtained from single crystal X-Ray diffraction studies of all three isomers reveal a difference in the relative orientation of the respective EtS-groups, while other commonly observed diastereomers as the result of cis-/trans- or fac-/mer-isomerism are not observed. Chemical exchange between the three diastereomers 2 a – c was discovered by phase-sensitive 1H and 31P NOESY NMR spectroscopy, and further quantified by line shape analysis of 1H NMR spectra. The experimentally derived averaged Gibbs energies of activation for the interconversion of the isomers (65–70 kJ/mol) are in good agreement with the results obtained from DFT calculations, which suggest an inversion of the ligating sulfur atoms, although a dissociative pathway for the configurational inversion can be competitive. 相似文献
810.