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971.
Zhilai Hong Arnaud Bolard Caroline Giraud Sbastien Prvost Grgory Genta‐Jouve Christiane Deregnaucourt Susanne Hussler Katy Jeannot Yanyan Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(10):3210-3214
Pseudomonas aeruginosa displays an impressive metabolic versatility, which ensures its survival in diverse environments. Reported herein is the identification of rare azetidine‐containing alkaloids from P. aeruginosa PAO1, termed azetidomonamides, which are derived from a conserved, quorum‐sensing regulated nonribosomal peptide synthetase (NRPS) pathway. Biosynthesis of the azetidine motif has been elucidated by gene inactivation, feeding experiments, and biochemical characterization in vitro, which involves a new S‐adenosylmethionine‐dependent enzyme to produce azetidine 2‐carboxylic acid as an unusual building block of NRPS. The mutants of P. aeruginosa unable to produce azetidomonamides had an advantage in growth at high cell density in vitro and displayed rapid virulence in Galleria mellonella model, inferring functional roles of azetidomonamides in the host adaptation. This work opens the avenue to study the biological functions of azetidomonamides and related compounds in pathogenic and environmental bacteria. 相似文献
972.
Min Tu Helge Reinsch Sabina Rodríguez‐Hermida Rhea Verbeke Timothe Stassin Werner Egger Marcel Dickmann Bjorn Dieu Johan Hofkens Ivo F. J. Vankelecom Norbert Stock Rob Ameloot 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2445-2449
Metal–organic frameworks (MOFs) enable the design of host–guest systems with specific properties. In this work, we show how the confinement of anthracene in a well‐chosen MOF host leads to reversible yellow‐to‐purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host–guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications. 相似文献
973.
Xing Huang Detre Teschner Maria Dimitrakopoulou Alexey Fedorov Benjamin Frank Ralph Kraehnert Frank Rosowski Harry Kaiser Stephan Schunk Christiane Kuretschka Robert Schlgl Marc‐Georg Willinger Annette Trunschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8801-8805
The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided. 相似文献
974.
Marcus B. Kindervater Katherine M. Marczenko Ulrike Werner‐Zwanziger Saurabh S. Chitnis 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7932-7937
Reaction of a tethered triamine ligand with Bi(NMe2)3 gives a Bi triamide, for which a BiI electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi?N and P?N bond polarities. Although considerable BiI character is indicated for the title Bi triamide, it exhibits reactivity similar to BiIII electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N‐oxide or W(CO)5. The product of the former shows evidence of coordination‐induced oxidation state change at bismuth. 相似文献
975.
976.
Felix Birkelbach Markus Deutsch Stylianos Flegkas Franz Winter Andreas Werner 《国际化学动力学杂志》2019,51(4):280-290
A method for deriving kinetic models of gas–solid reactions for reactor and process design is presented. It is based on the nonparametric kinetics (NPK) method and resolves many of its shortcomings by applying tensor rank-1 approximation methods. With this method, it is possible to derive kinetic models based on the general kinetic equation from any combination of experiments without additional a priori assumptions. The most notable improvements over the original method are that it is computationally much simpler and that it is not limited to two variables. Two algorithms for computing the rank-1 approximation as well as a tailored initialization method are presented, and their performance is assessed. Formulae for the variance estimation of the solution values are derived to improve the accuracy of the model identification and to provide a tool for diagnosing the quality of the kinetic model. The methods effectiveness and performance are assessed by applying it to a simulated data set. A Matlab implementation is available as Supporting Information. 相似文献
977.
Dr. Debabrata Maity Dr. Khaleel I. Assaf Wilhelm Sicking Dr. Christoph Hirschhäuser Prof. Dr. Werner M. Nau Prof. Dr. Carsten Schmuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13088-13093
A convenient supramolecular strategy for constructing a ratiometric fluorescent chemosensing ensemble, consisting of a macrocyclic host (cucurbit[8]uril CB[8]), and a pyrene-tagged amphiphilic peptide beacon (AP 1), is reported. AP 1 unfolds upon encapsulation of the pyrene termini into the hydrophobic CB[8] cavity. This changes pyrene excimer to monomer emission. Substrates with higher affinity for the CB[8] cavity can displace AP 1 from the ensemble. The released AP 1 folds again to form a pyrene excimer, which allows for the ratiometric fluorescence monitoring of the substrate. In this report, the ensemble capacity for ratiometric fluorescence monitoring of biological substrates, such as amino acid derivatives, specific peptides, and proteins, in aqueous media is demonstrated. 相似文献
978.
Niels Lichtenberger Werner Massa Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2019,58(10):3222-3226
We present the results from a reactivity study of the binary anion (TlBi3)2? towards Group 12 metal compounds MPh2 (M=Zn, Cd, Hg) to gain access to coordination compounds of polycyclic polypnictide molecules such as Bi73? or Bi113?. The coordination chemistry of these polybismuthide cages has been unprecedented to date, while it has been known for a long time for the lighter Group 15 anions Pn73? (Pn=P, As, Sb). The use of (TlBi3)2?, previously shown to release Tl under certain conditions in situ, resulted in the formation of the first heterometallic polyanion in which a nortricyclane‐type polybismuthide coordinates a transition‐metal atom, [(Bi7)Cd(Bi7)]4?. Reactions with the lighter Group 12 metal precursor yielded the uncommon ternary cluster [(Bi6)Zn3(TlBi5)]4?, most likely representing a reaction intermediate, and at the same time hinting at the formation of the nortricyclane‐shaped cage. Quantum‐chemical studies provide deeper insight into the stability trends of the [(E7)M(E7)]4? anion family and reveal a complex bonding situation in [(Bi6)Zn3(TlBi5)]4?, which features both localized and multi‐center bonding. 相似文献
979.
Michael Dmling Merle Arrowsmith Uwe Schmidt Luis Werner Abril C. Castro J. Oscar C. Jimnez‐Halla Rüdiger Bertermann Jonas Müssig Dominic Prieschl Holger Braunschweig 《Angewandte Chemie (International ed. in English)》2019,58(29):9782-9786
The transfer hydrogenation of N‐heterocyclic carbene (NHC)‐supported diborenes with dimethylamine borane proceeds with high selectivity for the trans‐1,2‐dihydrodiboranes. DFT calculations, supported by kinetic studies and deuteration experiments, suggest a stepwise proton‐first‐hydride‐second reaction mechanism via an intermediate μ‐hydrodiboronium dimethylaminoborate ion pair. 相似文献
980.
We present results on the fabrication and characterization of ridge waveguides in zinc-substituted lithium niobate. High-quality waveguides were fabricated by a combination of liquid-phase epitaxy and multiple applications of ion-beam enhanced etching. The two major demands on ridge waveguides, a very low side-wall roughness and a rectangle shape with side-wall angles close to 90 degrees , were realized simultaneously by using this technique. Single-mode waveguiding at a wavelength of 1064 nm was demonstrated with attenuation values of 0.9 dB/cm. 相似文献