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871.
The Oxidation of Thiols by Flavoprotein Oxidases: a Biocatalytic Route to Reactive Thiocarbonyls 下载免费PDF全文
Tom A. Ewing Willem P. Dijkman Prof. Dr. Jacques M. Vervoort Marco W. Fraaije Prof. Dr. Willem J. H. van Berkel 《Angewandte Chemie (International ed. in English)》2014,53(48):13206-13209
Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C? O, C? N, or C? C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C? S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioethers. Herein, we report that various flavoprotein oxidases, previously thought to solely act on alcohols, also catalyze the oxidation of thiols to thiocarbonyls. These results highlight the versatility of enzymatic catalysis and provide a potential biocatalytic route to reactive thiocarbonyl compounds, which have a variety of applications in synthetic organic chemistry. 相似文献
872.
873.
874.
Hydrogen Spillover Enhanced Hydroxyl Formation and Catalytic Activity Toward CO Oxidation at the Metal/Oxide Interface 下载免费PDF全文
Yuekang Jin Guanghui Sun Feng Xiong Liangbing Ding Prof. Dr. Weixin Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4252-4256
H2‐promoted catalytic activity of oxide‐supported metal catalysts in low‐temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt?FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low‐temperature CO oxidation, which provides a molecular‐level understanding of both H2‐promoted catalytic activity of metal/oxide ensembles in low‐temperature CO oxidation and hydrogen spillover. 相似文献
875.
Dr. Renata Kaczmarek Samuel Ward Dipra Debnath Taisiya Jacobs Alexander D. Stark Dariusz Korczyński Prof. Dr. Anil Kumar Prof. Dr. Michael D. Sevilla Dr. Sergey A. Denisov Dr. Viacheslav Shcherbakov Dr. Pascal Pernot Prof. Dr. Mehran Mostafavi Prof. Dr. Roman Dembinski Prof. Dr. Amitava Adhikary 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9495-9505
The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S−)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G.+-P(S−)=S. The ionization potential of G-P(S−)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G.+ to P(S−)=S led to dithiyl radical (P-2S.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S−)=S concentrations showed a bimolecular conversion of P-2S. to the σ2-σ*1-bonded dimer anion radical [-P-2S 2S-P-]− [ΔG (150 K, DFT)=−7.2 kcal mol−1]. However, [-P-2S 2S-P-]− formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol−1]. Neither P-2S. nor [-P-2S 2S-P-]− oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate. 相似文献
876.
Y. T. Angel Wong Vinicius Martins Dr. Bryan E. G. Lucier Prof. Dr. Yining Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):1848-1853
Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development. 相似文献
877.
Tao He Bin Li Li-Chuan Liu Jing Wang Wen-Peng Ma Guang-Yu Li Prof. Dr. Qing-Wei Zhang Prof. Dr. Wei He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(4):966-970
A copper-catalyzed trifunctionalization of alkynes that provides rapid access to oxindoles bearing a geminal diboronate side chain, highlighted by the simultaneous formation of one C−C bond and two C−B bonds, is reported. This new reaction features simple reaction conditions (ligand-free catalysis), a general substrate scope, and excellent chemoselectivity. Mechanistic study revealed a reaction sequence constituted by, in the order, borylation, intramolecular cross-coupling, hydroboration, which has been rarely documented. 相似文献
878.
Dr. Antony J. Stasyuk Dr. Olga A. Stasyuk Prof. Dr. Miquel Solà Prof. Dr. Alexander A. Voityuk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2577-2585
Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron-transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns−1. The formation of a long-living quinoxalinoporphyrin anion radical species is predicted. 相似文献
879.
Dr. Christoph Ludwig Teske Dr. Anna-Lena Hansen Prof. Dr. Richard Weihrich Prof. Dr. Lorenz Kienle Marius Kamp Kasper Pieter van der Zwan Prof. Dr. Jürgen Senker Dr. Carsten Dosche Prof. Dr. Gunther Wittstock Prof. Dr. Wolfgang Bensch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6763-6772
A new preparation route is developed for the synthesis of needle-like crystals of [Au(S2CNH2)2]SCN, which avoids disproportionation of the AuI salt used as a starting material. In the crystal structure, the two crystallographically independent AuIII centers are in a square-planar environment of two S2CNH2 ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)2N. 13C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles. 相似文献
880.
Jia-Bin Han Ao Guo Prof. Xiang-Ying Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):2989-2994
A challenging deoxygenation of alkoxyl radicals from readily accessible alcohol derivatives was developed, affording facile synthesis of functionalized alkenes with good functional group tolerance under mild reaction conditions. Because alkoxyl radicals can easily undergo β-fragmentations or hydrogen abstractions, this new strategy for deoxygenation of alkoxyl radicals is highly valuable. Moreover, mechanistic studies revealed that the electron-neutral phosphine acts as the deoxygenation reagent. 相似文献