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901.
Edward L. Briggs Arianna Tota Marco Colella Leonardo Degennaro Renzo Luisi James A. Bull 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14441-14448
Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ6‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles. 相似文献
902.
Marco Carini Mauro Marongiu Karol Strutyski Akinori Saeki Manuel Melle‐Franco Aurelio Mateo‐Alonso 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(44):15935-15939
Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties. 相似文献
903.
Alice E. Dearle Daniel J. Cutler Hector W. L. Fraser Sergio Sanz Edward Lee Sourav Dey Ismael F. Diaz‐Ortega Gary S. Nichol Hiroyuki Nojiri Marco Evangelisti Gopalan Rajaraman Jürgen Schnack Leroy Cronin Euan K. Brechin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(47):17059-17062
The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe34] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral FeIII ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe34], bulk iron oxides, previous FeIII–oxo cages, and polyoxometalates (POMs), hints that much larger molecular FeIII oxides can be made. 相似文献
904.
905.
Qijun Meng Biaobiao Zhang Lizhou Fan Haidong Liu Mario Valvo Kristina Edstrm Maria Cuartero Roland de Marco Gaston A. Crespo Licheng Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):19203-19209
Water‐splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co‐catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, a simple treatment is reported that involves soaking a sample of pristine BiVO4 in a borate buffer solution. This modifies the catalytic local environment of BiVO4 by the introduction of a borate moiety at the molecular level. The self‐anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO4 photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5 mA cm?2 at 1.23 V and a cathodically shifted onset potential of 250 mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO4 photoanodes. 相似文献
906.
Donald Hill Peter J. Holliman Eurig W. Jones James McGettrick David A. Worsley Marco Appleman Pranesh Chatterjee 《Surface and interface analysis : SIA》2019,51(9):934-942
This paper studies the removal of chemisorbed carboxylates and phosphonates from TiO2-coated galvanized steel using NaOH(aq). XPS and FTIR data show that NaOH(aq) is effective at desorbing these species and so is an alternative to gas phase processes (eg, plasma cleaning). Tribological investigations show that NaOH(aq)-treated surfaces show reduced friction and wear, relative to the “as-received” galvanized steel. This is ascribed to carbonate (present as an impurity in NaOH) that adsorbs to the surface of the substrate during NaOH(aq) immersion. Carbonate removal through sonication in water generates surfaces that show friction similar to “as-received” galvanized steel. This work is useful in areas (eg, automotive manufacturing), where the effective removal of lubricants following tribological contact is key to subsequent paint adhesion. 相似文献
907.
908.
Juan Sanz García Martial Boggio-Pasqua Ilaria Ciofini Marco Campetella 《Journal of computational chemistry》2019,40(14):1420-1428
The ability to locate minima on electronic excited states (ESs) potential energy surfaces both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic ESs close in energy, but also due to the complex nature of the ESs involved. In this article, we present a simple yet powerful method to follow an ES of interest during a structural optimization in the case of TMCs, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wave function overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium nitrosyl complex which is very problematic with standard approaches. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc. 相似文献
909.
Dao Le Marco Dilger Vincent Pertici Silvia Diabat Didier Gigmes Carsten Weiss Guillaume Delaittre 《Angewandte Chemie (International ed. in English)》2019,58(14):4725-4731
We report the straightforward, time‐efficient synthesis of radical core–shell nanoparticles (NPs) by polymerization‐induced self‐assembly. A nitroxide‐containing hydrophilic macromolecular precursor was prepared by ring‐opening metathesis copolymerization of norbornenyl derivatives of TEMPO and oligoethylene glycol and was chain‐extended in situ with norbornene in ethanolic solution, leading to simultaneous amphiphilic block copolymer formation and self‐assembly. Without any intermediate purification from the monomers to the block copolymers, radical NPs with tunable diameters ranging from 10 to 110 nm are obtained within minutes at room temperature. The high activity of the radical NPs as chemoselective and homogeneous, yet readily recyclable catalysts is demonstrated through oxidation of a variety of alcohols and recovery by simple centrifugation. Furthermore, the NPs show biocompatibility and antioxidant activity in vitro. 相似文献
910.
Monica Averna Alessandro A. Casazza Antonino Martines Marco Pedrazzi Alice Franchi Roberta De Tullio 《Natural product research》2019,33(10):1449-1455
We are reporting in the present study that molecules extracted from olive pomace prevent cell death induced by Ca2+-overloading in different cell types. Exposure of cells to these molecules counteracts the Ca2+-induced cell damages by reducing the activation of the Ca2+-dependent protease calpain, acting possibly through the modification of the permeability to Ca2+ of the plasma membrane. The purification step by RP-HPLC suggests that effective compound(s), differing from the main biophenols known to be present in the olive pomace extract, could be responsible for this effect. Our observations suggest that bioactive molecules present in the olive pomace could be potential candidates for therapeutic applications in pathologies characterised by alterations of intracellular Ca2+ homeostasis. 相似文献