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排序方式: 共有1311条查询结果,搜索用时 15 毫秒
1.
Prof. James S. M. Anderson Prof. Juan I. Rodríguez Prof. Paul W. Ayers Daniel E. Trujillo-González Dr. Andreas W. Götz Prof. Jochen Autschbach Prof. Fray L. Castillo-Alvarado Prof. Koichi Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2538-2544
The topology of the molecular electron density of benzene dithiol gold cluster complex Au4−S−C6H4−S′−Au′4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization. 相似文献
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Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes 下载免费PDF全文
Nidal Saleh Barry Moore II Monika Srebro Nicolas Vanthuyne Loïc Toupet J. A. Gareth Williams Christian Roussel Kirandeep K. Deol Gilles Muller Jochen Autschbach Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1673-1681
Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation. 相似文献
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Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties 下载免费PDF全文
Dr. Mehdi El Sayed Moussa Dr. Hui Chen Zuoyong Wang Dr. Monika Srebro‐Hooper Dr. Nicolas Vanthuyne Dr. Soizic Chevance Prof. Christian Roussel Prof. J. A. Gareth Williams Prof. Jochen Autschbach Prof. Régis Réau Prof. Zheng Duan Dr. Christophe Lescop Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6075-6086
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b . 相似文献
7.
Dennis Jansen Johannes Gramüller Felix Niemeyer Torsten Schaller Matthias C. Letzel Stefan Grimme Hui Zhu Ruth M. Gschwind Jochen Niemeyer 《Chemical science》2020,11(17):4381
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration. 相似文献
8.
Myriam Drouin Dr. Parvesh Wadhwani Dr. Stephan L. Grage Dr. Jochen Bürck Dr. Johannes Reichert Sébastien Tremblay Marie Sabine Mayer Christian Diel Alexander Staub Prof. Jean-François Paquin Prof. Dr. Anne S. Ulrich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1511-1517
Solid-state 19F NMR is a powerful method to study the interactions of biologically active peptides with membranes. So far, in labelled peptides, the 19F-reporter group has always been installed on the side chain of an amino acid. Given the fact that monofluoroalkenes are non-hydrolyzable peptide bond mimics, we have synthesized a monofluoroalkene-based dipeptide isostere, Val-Ψ[(Z)-CF=CH]-Gly, and inserted it in the sequence of two well-studied antimicrobial peptides: PGLa and (KIGAKI)3 are representatives of an α-helix and a β-sheet. The conformations and biological activities of these labeled peptides were studied to assess the suitability of monofluoroalkenes for 19F NMR structure analysis. 相似文献
9.
Ceren Kütahya Nicolai Meckbach Prof. Dr. Veronika Strehmel Prof. Dr. Jochen S. Gutmann Prof. Dr. Bernd Strehmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10444-10451
NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [CuII/(TPMA)]Br2 (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol. 相似文献
10.
Bruno Voigt Twinkle Bhatia Julia Hesselbarth Dr. Monika Baumann Prof. Dr. Carla Schmidt Dr. Maria Ott Prof. Dr. Jochen Balbach 《Chemphyschem》2023,24(19):e202300439
Nucleation and growth of amyloid fibrils were found to only occur in supersaturated solutions above a critical concentration (ccrit). The biophysical meaning of ccrit remained mostly obscure, since typical low values of ccrit in the sub-μM range hamper investigations of potential oligomeric states and their structure. Here, we investigate the parathyroid hormone PTH84 as an example of a functional amyloid fibril forming peptide with a comparably high ccrit of 67±21 μM. We describe a complex concentration dependent prenucleation ensemble of oligomers of different sizes and secondary structure compositions and highlight the occurrence of a trimer and tetramer at ccrit as possible precursors for primary fibril nucleation. Furthermore, the soluble state found in equilibrium with fibrils adopts to the prenucleation state present at ccrit. Our study sheds light onto early events of amyloid formation directly related to the critical concentration and underlines oligomer formation as a key feature of fibril nucleation. Our results contribute to a deeper understanding of the determinants of supersaturated peptide solutions. In the current study we present a biophysical approach to investigate ccrit of amyloid fibril formation of PTH84 in terms of secondary structure, cluster size and residue resolved intermolecular interactions during oligomer formation. Throughout the investigated range of concentrations (1 μM to 500 μM) we found different states of oligomerization with varying ability to contribute to primary fibril nucleation and with a concentration dependent equilibrium. In this context, we identified the previously described ccrit of PTH84 to mark a minimum concentration for the formation of homo-trimers/tetramers. These investigations allowed us to characterize molecular interactions of various oligomeric states that are further converted into elongation competent fibril nuclei during the lag phase of a functional amyloid forming peptide. 相似文献