Copper(II)‐Coordinated α‐Azophenols: Effect of the Metal‐Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity

Kochem, Amélie; Carrillo, Alexandre; Philouze, Christian; Gastel, Maurice van; d′Hardemare, Amaury du Moulinet; Thomas, Fabrice

doi:10.1002/ejic.201402312

Cited by 14 publications

(10 citation statements)

References 20 publications

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“…In agreement with the implications of the XRD‐derived structure, the absorption maximum in the reflectance mode at 607 nm indicated a distorted square pyramidal or nearly square‐planar coordination sphere . Similar conclusions hold for the spectra in solution, in which the recorded maximum at λ =610 nm falls between data typical of square‐planar (555 nm< λ <575 nm) and square‐pyramidal coordination (620 nm< λ <675 nm).…”

Section: Resultssupporting

confidence: 80%

Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity

Gülzow

Hörner

Strauch

et al. 2017

Chemistry A European J

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What is the most significant result of this study? Attempts to mimic metalloenzymes teach us about catalysis, and the lessons learnt find widespread application in an umber of chemical disciplines, including process engineering. Our catechol oxidase models show an unprecedented dependence of their reactivity on the method of oxygen administration:w hen going beyond the limits of homogeneously distributed reactants, by administering surplus dioxygen periodically during catalytic turnover, we observed reactivities increasing by factors of five to ten, in comparison with the well-established conditions of dioxygen saturation. This observation is not limited to our new system. Reference experiments with systems taken from the literature suggest that the effect, which is of interest in the context of reactive bubbly flows, is general, but has hitherto gone unnoticed. What was the inspiration for this cover design? When we were invited to submit ad esign, we took inspiration from the fact that the browning of cut fruit is effected by copper-and oxygen-dependent oxygenases, leading to melanine pigments, which are polymeric ortho-quinone derivatives. An abstract rendering of our dinuclear copper(II) complexes is shown in the foreground at left. In our cover art, as till life by Gabriele Endres, the browning of the half-eaten apple in the foreground denotes the enhanced reaction of our model substrate, ac atechol, under oxygen-enriched conditions, as provided by ab ubbly flow of oxygen. What other topics are you working on at the moment? We are interested in the activation of dioxygen and its exploitation as an environmentally benign, or green, oxidant, using bioinspired transition-metal complexes of tailor-made ligands. Our "workhorse" metal ions are iron and copper,i nt heir various oxidation states, and we are currently making our first forays into the coordination chemistry of manganese. Our ligands are polypodal, including tetra-and pentadentate ligands, as in the present work, or extended -tripodal hexadentate, as in recent spin-state dynamics studies. The former chelators shield am ajor part of the metal-coordination sphere, focusing the reactivity on one or two "labile" coordination sites. The coordinative strain of all these claw-like ligands can also be varied, enabling investigations, in which distortions of the coordination sphere and their influence on complex reactivity and spin multiplicity,c an be studied in isolation (and with reference to the concept of the entatic state). Invited for the cover of this issue is the group of Gerald Hçrner and Andreas Grohmann at the Technical University of Berlin. The image depicts that the browning of cut fruit is effected by copper-and oxygen-dependent oxygenases, leading to mela-nine pigments, which are polymeric ortho-quinone derivatives.R ead the full text of the article at

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Section: Resultssupporting

confidence: 80%

Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity

Gülzow

Hörner

Strauch

et al. 2017

Chemistry A European J

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“…The starting compounds of 2-methylquinolin-8-amine [ 24 ], and 7-methylquinolin-8-amine [ 25 ] were prepared using the reported methods. 4-Amino- N -(5-methylisoxazol-3-yl)benzenesulfonamide ( I ), 4-amino- N -(pyridin-2-yl)benzenesulfonamide ( II ), 4-amino- N -(pyrimidin-2-yl)benzenesulfonamide ( III ), 4-amino- N -(4-methylpyrimidin-2-yl)benzenesulfonamide ( IV ), 4-amino- N -(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide ( V ), 4-amino- N -(2,6-dimethoxypyrimidin-4-yl)benzenesulfonamide ( VI ), and 4-amino- N -(6-methoxypyridazin-3-yl)benzenesulfonamide ( VII ) were commercially available.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Molecular Structure, Anticancer Activity, and QSAR Study of N-(aryl/heteroaryl)-4-(1H-pyrrol-1-yl)Benzenesulfonamide Derivatives

Żołnowska

Sławiński

Brzozowski

et al. 2018

IJMS

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A series of N-(aryl/heteroaryl)-4-(1H-pyrrol-1-yl)benzenesulfonamides were synthesized from 4-amino-N-(aryl/heteroaryl)benzenesulfonamides and 2,5-dimethoxytetrahydrofuran. All the synthesized compounds were evaluated for their anticancer activity on HeLa, HCT-116, and MCF-7 human tumor cell lines. Compound 28, bearing 8-quinolinyl moiety, exhibited the most potent anticancer activity against the HCT-116, MCF-7, and HeLa cell lines, with IC50 values of 3, 5, and 7 µM, respectively. The apoptotic potential of the most active compound (28) was analyzed through various assays: phosphatidylserine translocation, cell cycle distribution, and caspase activation. Compound 28 promoted cell cycle arrest in G2/M phase in cancer cells, induced caspase activity, and increased the population of apoptotic cells. Relationships between structure and biological activity were determined by the QSAR (quantitative structure activity relationships) method. Analysis of quantitative structure activity relationships allowed us to generate OPLS (Orthogonal Projections to Latent Structure) models with verified predictive ability that point out key molecular descriptors influencing benzenosulfonamide’s activity.

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“…Benisvy et al reported a number of complexes of pyrazole/imidazole-phenolate with Cu, Co or Zn [11][12][13][14][15][16]. Kochem et al reported [18] a system highlighting the effect of steric strain in the Cu complex on the phenolate/phenoxyl oxidation process.…”

Section: Introductionmentioning

confidence: 96%

Acid–base behavior, electrochemical properties and DFT study of redox non-innocent phenol–imidazole ligands and their Cu complexes

et al. 2015

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Copper(II)‐Coordinated α‐Azophenols: Effect of the Metal‐Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity

Abstract: International audienc

Cited by 14 publications

References 20 publications

Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity

Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity

Synthesis, Molecular Structure, Anticancer Activity, and QSAR Study of N-(aryl/heteroaryl)-4-(1H-pyrrol-1-yl)Benzenesulfonamide Derivatives

Acid–base behavior, electrochemical properties and DFT study of redox non-innocent phenol–imidazole ligands and their Cu complexes

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