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101.
We have studied the effect of interface heterogeneity on fracture, at both local and global scales. The single cantilever beam adhesion test was used to investigate interfacial fracture between polycarbonate plates and an elastic/fragile epoxy adhesive. Two surface treatments were applied to a (given) polycarbonate plate giving zones of strong and weak adhesion parallel to the crack direction. Calculated fracture energies differed from those expected from a simple rule-of-mixtures. A perturbation method, proposed by Rice, was used and results compared with crack fronts observed in situ. The technique was applied successfully but the difference in values of stress intensity factor between the zones was found substantially different from the experimental value. In an attempt to explain discrepancies, specimens with discontinuous crack fronts (adhesive and/or plates severed along the strong/weak adhesion frontier) were tested. Good agreement was found with the rule-of-mixtures predictions raising questions about the role of crack front continuity in load transfer. 相似文献
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Dr. Jan Vícha Dr. Petr Švec Dr. Zdeňka Růžičková Dr. Maksim A. Samsonov Kateřina Bártová Prof. Aleš Růžička Dr. Michal Straka Dr. Martin Dračínský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8698-8702
Spin-orbit (SO) heavy-atom on the light-atom (SO-HALA) effect is the largest relativistic effect caused by a heavy atom on its light-atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1H, 13C, and 15N nuclei. In this study, a combined experimental and theoretical evidence for the SO-HALA effect transmitted through hydrogen bond is presented. Solid-state NMR data for a series of 4-dimethylaminopyridine salts containing I−, Br− and Cl− counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO-HALA effect through hydrogen bonds. 相似文献
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Dr. Laura Ielo Prof. Dr. Vittorio Pace Prof. Dr. Wolfgang Holzer Md. Mahbubur Rahman Dr. Guangrong Meng Dr. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16246-16250
The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to nN→π*C=O conjugation. In this study, we report electrophilicity scale by exploiting 17O NMR and 15N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds. 相似文献
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Dr. Jana Hudecová Dr. Josef Kapitán Prof. Martin Dračínský Pavel Michal Dr. Václav Profant Prof. Petr Bouř 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202045
The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis2 complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis2 is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems. 相似文献
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