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151.
Steffen Dachwitz Bjarne Scharkowski Prof. Norbert Sewald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18043-18046
Mild transition-metal catalysed cross-couplings enable direct functionalisation of biocatalytically halogenated tryptophans with alkyl iodides, representing a new alternative for late-stage derivatisations of halogenated aromatic amino acids. Moreover, this strategy enables preparation of (homo)tryptophan regioisomers in a simple two-step synthesis using a Pd-catalysed Negishi cross coupling. This method provides access to non-canonical constitutional surrogates of tryptophan, ready for use in peptide synthesis. 相似文献
152.
Dr. Mostakim SK Dr. Soumitra Barman Shounik Paul Ratnadip De Dr. S. S. Sreejith Dr. Helge Reinsch Dr. Maciej Grzywa Dr. Norbert Stock Prof. Dr. Dirk Volkmer Dr. Shyam Biswas Prof. Dr. Soumyajit Roy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(12):4098-4107
A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h−1 in addition to oxygen, which was produced with a TOF of 0.54 h−1. No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here. 相似文献
153.
Dr. Philipp Holtkamp Dario Poier Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3793-3798
The reactivity of the geminal frustrated Lewis pair (FLP) (F5C2)3SnCH2P(tBu)2 ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3CC(O)CH=CH2, Ph[C(O)]2Ph, PhN=NPh and Me3SiCHN2), featuring polar or non-polar multiple bonds and/or represent α,β-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu)2PCH2-transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments. 相似文献
154.
Dieter Leibfritz Erhard Haupt Norbert Dubischar Heinrich Lachmann Raymond Oekonomopulos Günther Jung 《Tetrahedron》1982,38(14):2165-2181
The uncommon amino-acid 2-methylalanine (α-aminoisobutyric acid, Aib) was investigated by 13C-NMR. The chemical shifts of amino- or carboxy-protected derivatives of Aib and of protected oligopeptides are discussed with respect to neighbouring groups and amino acids. The pH-dependence of the 13C-NMR spectra of Aib, Aib-Ala, Ala-Aib, Aib-Ala-Aib and Aib-Ala-Aib-Ala-Aib was studied. Using these examples, a new and advantageous method is demonstrated for the first time for the evalutions of NMR titration curves, which uses so-called chemical shift diagrams (CS diagrams). 相似文献
155.
Dr. Julia Kratky Daniel Eggerichs Dr. Thomas Heine Sarah Hofmann Philipp Sowa Dr. Renato H. Weiße Prof. Dr. Dirk Tischler Prof. Dr. Norbert Sträter 《Angewandte Chemie (International ed. in English)》2023,62(17):e202303193
Flavoprotein monooxygenases are a versatile group of enzymes for biocatalytic transformations. Among these, group E monooxygenases (GEMs) catalyze enantioselective epoxidation and sulfoxidation reactions. Here, we describe the crystal structure of an indole monooxygenase from the bacterium Variovorax paradoxus EPS, a GEM designated as VpIndA1. Complex structures with substrates reveal productive binding modes that, in conjunction with force-field calculations and rapid mixing kinetics, reveal the structural basis of substrate and stereoselectivity. Structure-based redesign of the substrate cavity yielded variants with new substrate selectivity (for sulfoxidation of benzyl phenyl sulfide) or with greatly enhanced stereoselectivity (from 35.1 % to 99.8 % ee for production of (1S,2R)-indene oxide). This first determination of the substrate binding mode of GEMs combined with structure-function relationships opens the door for structure-based design of these powerful biocatalysts. 相似文献
156.
Johannes Oschwald Dr. David Reger Dr. Stefan Frühwald Vera Warmbrunn Prof. Dr. Andreas Görling Prof. Dr. Norbert Jux Prof. Dr. Thomas Drewello 《Chemphyschem》2023,24(21):e202300496
Gas-phase complexes of [n]helicenes with n=6, 7 and 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI-MS). Besides the well-established [1 : 1] helicene/Ag+-complex in which the helicene provides a tweezer-like surrounding for the Ag+, there is also a [2 : 1] complex formed. Density functional theory (DFT) calculations in conjunction with energy-resolved collision-induced dissociation (ER-CID) experiments reveal that the second helicene attaches via π-π stacking to the first helicene, which is part of the pre-formed [1 : 1] tweezer complex with Ag+. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2 : 1] complex with silver(I) is typically structured as an Ag+-bound dimer in which the Ag+ would bind to both PAHs as the central metal ion (PAH–Ag+–PAH). For helicenes, the Ag+-bound dimer is of similar thermochemical stability as the π-π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison to the helicenes as an essentially planar PAH. In analogy to the π-π stacked dimer of the helicenes, the Cor−Ag+−Cor−Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag+ are preferably formed with the larger helicenes, with n=6 being entirely ignored as the host for Ag+ in the presence of n=7 or 8. 相似文献
157.
Matthias Mawick Carolin Jaworski Jens Bittermann Dr. Ljuba Iovkova Yinglan Pu Prof. Dr. Carmen Wängler Prof. Dr. Björn Wängler Prof. Dr. Klaus Jurkschat Prof. Dr. Norbert Krause Prof. Dr. Ralf Schirrmacher 《Angewandte Chemie (International ed. in English)》2023,62(50):e202309002
The ring-opening Si-fluorination of a variety of azasilole derivatives cyclo-1-(iPr2Si)−4-X−C6H3−2-CH2NR ( 4 : R=2,6-iPr2C6H3, X=H; 4 a : R=2,4,6-Me3C6H2, X=H; 9 : R=2,6-iPr2C6H3, X=tBuMe2SiO; 10 : R=2,6-iPr2C6H3, X=OH; 13 : R=2,6-iPr2C6H3, X=HCCCH2O; 22 : R=2,6-iPr2C6H3, X=tBuMe2SiCH2O) with different 19F-fluoride sources was studied, optimized and the experience gained was used in a translational approach to create a straightforward 18F-labelling protocol for the azasilole derivatives [18F] 6 and [18F] 14 . The latter constitutes a potential clickable CycloSiFA prosthetic group which might be used in PET tracer development using Cu-catalysed triazole formation. Based on our findings, CycloSiFA has the potential to become a new entry into non-canonical labelling methodologies for radioactive PET tracer development. 相似文献
158.
159.
We consider the Riemannian universal covering of a compact manifold M = X/ and assume that is amenable. We show the existence of a (nonrandom) integrated density of states for an ergodic random family of Schrödinger operators on X. 相似文献
160.
Hegedus L Kirschner N Wittmann M Simon P Noszticzius Z Amemiya T Ohmori T Yamaguchi T 《Chaos (Woodbury, N.Y.)》1999,9(2):283-297
The polarization curve of an acid-base interface in a hydrogel medium has a diode characteristic. Two of each such electrolyte diodes can be combined to give an electrolyte transistor. When a salt is added to the alkaline or to the acidic part of a reverse biased electrolyte diode, the current response is highly nonlinear. If the salt is added to the acidic side, even bistability can be observed. This bistability can generate complex oscillations in a base-acid-base electrolyte transistor. These nonlinear effects are studied experimentally and theoretically. While the nonlinear salt effect can be explained with the Nernst-Planck equations, to understand the bistable behavior further investigations are necessary. (c) 1999 American Institute of Physics. 相似文献