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排序方式: 共有274条查询结果,搜索用时 15 毫秒
1.
Dr. Jifu Duan Dr. Anja Hemschemeier David J. Burr Dr. Sven T. Stripp Prof. Eckhard Hofmann Prof. Thomas Happe 《Angewandte Chemie (International ed. in English)》2023,62(7):e202216903
Hydrogenases are H2 converting enzymes that harbor catalytic cofactors in which iron (Fe) ions are coordinated by biologically unusual carbon monoxide (CO) and cyanide (CN−) ligands. Extrinsic CO and CN−, however, inhibit hydrogenases. The mechanism by which CN− binds to [FeFe]-hydrogenases is not known. Here, we obtained crystal structures of the CN−-treated [FeFe]-hydrogenase CpI from Clostridium pasteurianum. The high resolution of 1.39 Å allowed us to distinguish intrinsic CN− and CO ligands and to show that extrinsic CN− binds to the open coordination site of the cofactor where CO is known to bind. In contrast to other inhibitors, CN− treated crystals show conformational changes of conserved residues within the proton transfer pathway which could allow a direct proton transfer between E279 and S319. This configuration has been proposed to be vital for efficient proton transfer, but has never been observed structurally. 相似文献
2.
Coumarin-based urea and urea–amide scaffolds 1–3 have been designed and synthesized for the selective and naked eye detection of cyanide ion. Of the three, compound 3 exhibits ratiometric fluorescence change selectively in the presence of CN? and validates the rationality in designing anion receptor. Upon interaction with CN?, the color of the solution of 3 in CH3CN under UV exposure becomes bright yellow, which is beneficial for its naked eye detection. Addition of CN? of ~10?4 M brings nice color change from colourless to yellow in ordinary light. The sensing event is supposed to be due to nucleophilic addition of CN? to the coumarin unit enabling intramolecular charge transfer (ICT) mechanism. 相似文献
3.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(2):606-609
Co‐crystallization of a cyanide‐bridged tetranuclear complex [Co2Fe2] with 4‐cyanophenol (CP) gave a hydrogen bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2 CP⋅8 BN ( 1 ). 1 exhibited a three‐step phase transition between HT, IM1, IM2, and LT phases upon temperature variation. Variable temperature magnetic measurements and structural analyses revealed that the three‐step spin transition is caused by electron‐transfer‐coupled spin transitions (ETCSTs) accompanied with alteration of the hydrogen bonding interactions. 相似文献
4.
《Comptes Rendus Chimie》2017,20(4):415-423
The optical and colorimetric properties of a new chemosensor 4-((2,4-dichlorophenyl)diazenyl)-2-(3-hydroxypropylimino)methyl)phenol (L) for cyanide ions were investigated by the naked-eye detection and UV–vis spectroscopy. This receptor reveals visual changes toward CN− anions in aqueous media. No significant color changes were observed upon the addition of any other anions. The cyanide recognition properties of the receptor through proton-transfer were monitored by UV–vis titration and 1H NMR spectroscopy. The binding constant (Ka) and stoichiometry of the formed host–guest complex were calculated by the Benesi–Hildebrand (B–H) plot and Job's plot method, respectively. The detection limit of the probe towards CN− was 1.03 × 10−6 mol L−1, which is lower than the maximum value of cyanide (1.9 × 10−6 mol L−1) permitted by the World Health Organization in drinking water. Thus, this chemosensor was sensitive enough to detect cyanide in aqueous solutions. 1H NMR experiments were conducted to investigate the nature of interaction between the receptor and CN− anions. Notably, the designed sensor can be applied for the rapid detection of cyanide anions in the basic pH range and also under physiological conditions, for practical purposes for a long duration. The sensing behavior of the receptor was further emphasized by computational studies. Quantum-chemical calculations and molecular studies via Density Functional Theory (DFT) were carried out to supplement the experimental results. 相似文献
5.
《印度化学会志》2021,98(12):100230
The present study aims at efficient abatement of pollutants from coke-oven wastewater using environment-friendly and low-cost adsorbents for a green world. The adsorbent used were native laterite soil (NLS), heat-treated laterite soil (HTLS), native shale (NS) and Heat-treated shale (HTS). One factor at a time (OFAT) approach was followed to determine the most effective condition based on the maximum removal. Heat-treated laterite soil and native shale were found most effective among their counterparts. Freundlich model was found best to analyze equilibrium data. The real coke-oven wastewater was collected and experiments were performed in batch mode. The percentage removal of cyanide (88.09% and 95.31%) and ammoniacal-N (87.28% and 92.12%) were found satisfactory when heat-treated laterite soil and native shale were used as adsorbents, respectively. 相似文献
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Makoto Nonomura Fumio Nakagawa Shinya Mizusawa Takashi Ohno Hiroyuki Kobayashi Toshiyuki Hobo 《International journal of environmental analytical chemistry》2013,93(4):371-379
Abstract Although cyanide compounds are not incorporated in photographic processing solutions, false detection of cyanide ion is often encountered during the determination of total cyanide by various standardized methods such as ISO, ANSI and JIS. Various organic compounds and nitrogen compounds in the processing solutions were examined because of this false detection. The results suggest that hydrogen cyanide is formed by a reaction between these compounds during the distillation process for the separation of total cyanide, even though ISO, ANSI and JIS were used. The results support the following three mechanisms of cyanide formation involved in the process: (1) Hydroxylammonium salts reacts with another ingredient, formaldehyde, to form formaldoxime, which then decomposes to HCN. (2) Hydroxylammonium is oxidized by air to form nitrite ion, which subsequently reacts with organic compounds such as aminocarboxylic acids and aromatic amines (the colour-developing agent) to form HCN. (3) Potassium permanganate oxidizes aromatic amines to form HCN. 相似文献
9.
Xinghui Qi Dr. Sébastien Pillet Dr. Coen de Graaf Michał Magott Dr. El-Eulmi Bendeif Dr. Philippe Guionneau Dr. Mathieu Rouzières Dr. Valérie Marvaud Dr. Olaf Stefańczyk Dr. Dawid Pinkowicz Dr. Corine Mathonière 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3141-3145
The photoinduced properties of the octacoordinated complex K4MoIV(CN)8⋅2 H2O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light-induced cleavage of one Mo−CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt-222)]3[MoIV(CN)7]⋅3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution. 相似文献
10.
利用含时密度泛函方法计算了两个具有类似结构的传感器分子a和b的氰离子传感机理. 结果证实,传感器分子a在基态和S1态下有着类似的几何构型. 在质子性溶剂水中,氰离子能与传感器分子a发生Michael加成反应,水溶液提供质子,促使最终的α,β-加成产物的生成. 而此加成产物在S1态下会发生构型变化,导致荧光的猝灭. 传感器分子b的S1态与基态构型相比发生了构型扭转,并且在非质子性溶剂乙腈中,也可以与氰离子发生Michael加成反应. 由于乙腈 相似文献