scholarly journals Expanding the reactivity of inorganic clusters towards proteins: the interplay between the redox and hydrolytic activity of Ce(iv)-substituted polyoxometalates as artificial proteases

2021 ◽  
Author(s):  
Shorok A. M. Abdelhameed ◽  
Hong Giang T. Ly ◽  
Jens Moons ◽  
Francisco de Azambuja ◽  
Paul Proost ◽  
...  
Keyword(s):  
Redox Chemistry ◽  
Hydrolytic Activity ◽  
Reaction Parameters ◽  
Protein Surface ◽  
Redox Active ◽  
Inorganic Clusters

The redox chemistry of CeIV-polyoxometalates towards proteins is linked to the redox-active residues on protein surface. It can be tuned by adjusting reaction parameters, directly impacting its efficiency and selectivity as an artificial protease.

Redox chemistry of CeO2 nanoparticles in aquatic systems containing Cr(vi)(aq) and Fe2+ ions

2019 ◽  
Vol 6 (7) ◽  
pp. 2269-2280
Author(s):  
Jessica R. Ray ◽  
Xuanhao Wu ◽  
Chelsea W. Neil ◽  
Haesung Jung ◽  
Zhichao Li ◽  
...  
Keyword(s):  
Surface Chemistry ◽  
Redox Chemistry ◽  
Industrial Applications ◽  
Active Species ◽  
Ceo2 Nanoparticles ◽  
Aquatic Systems ◽  
Aquatic Environments ◽  
Catalytic Activities ◽  
Redox Active

CeO2 nanoparticles are extensively used in industrial applications owing to their high redox-catalytic activities and, as a result, may appear in aquatic environments where they undergo significant surface chemistry transformation with other redox-active species.

scholarly journals Synthesis and ligand-based reduction chemistry of boron difluoride complexes with redox-active formazanate ligands

2014 ◽  
Vol 50 (56) ◽  
pp. 7431-7433 ◽  
Author(s):  
M.-C. Chang ◽  
E. Otten
Keyword(s):  
Boron Trifluoride ◽  
Redox Chemistry ◽  
Zinc Complexes ◽  
Redox Active ◽  
Boron Difluoride

Mono(formazanate) boron difluoride complexes (LBF2), which show remarkably facile and reversible ligand-based redox-chemistry, were synthesized by transmetallation of bis(formazanate) zinc complexes with boron trifluoride.

Cobalt complexes of octaethyloxophlorin. Metal-centered redox chemistry in the presence of a redox-active ligand

1993 ◽  
Vol 32 (22) ◽  
pp. 4737-4744 ◽  
Author(s):  
Alan L. Balch ◽  
Marinella Mazzanti ◽  
Marilyn M. Olmstead
Keyword(s):  
Cobalt Complexes ◽  
Redox Chemistry ◽  
Redox Active Ligand ◽  
Active Ligand ◽  
Redox Active

scholarly journals Reversible Redox Chemistry and Catalytic C(sp3)–H Amination Reactivity of a Paramagnetic Pd Complex Bearing a Redox-Active o-Aminophenol-Derived NNO Pincer Ligand

2016 ◽  
Vol 55 (17) ◽  
pp. 8603-8611 ◽  
Author(s):  
Daniël L. J. Broere ◽  
Nicolaas P. van Leest ◽  
Bas de Bruin ◽  
Maxime A. Siegler ◽  
Jarl Ivar van der Vlugt
Keyword(s):  
Redox Chemistry ◽  
Pincer Ligand ◽  
Redox Active ◽  
Reversible Redox

Mutagenesis of the redox-active disulfide in mercuric ion reductase: catalysis by mutant enzymes restricted to flavin redox chemistry

Biochemistry ◽  
1989 ◽  
Vol 28 (3) ◽  
pp. 1168-1183 ◽  
Author(s):  
Mark D. Distefano ◽  
Karin G. Au ◽  
Christopher T. Walsh
Keyword(s):  
Redox Chemistry ◽  
Mercuric Ion ◽  
Redox Active

scholarly journals Nanodiamond surface redox chemistry: influence of physicochemical properties on catalytic processes

2014 ◽  
Vol 172 ◽  
pp. 349-364 ◽  
Author(s):  
Thomas S. Varley ◽  
Meetal Hirani ◽  
George Harrison ◽  
Katherine B. Holt
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Physicochemical Properties ◽  
Redox Chemistry ◽  
Redox Species ◽  
Redox Active ◽  
Ph Dependent ◽  
Catalytic Processes ◽  
Surface Redox

Modification of an electrode with an immobilised layer of nanodiamond is found to significantly enhance the recorded currents for reversible oxidation of ferrocene methanol (FcMeOH). Current enhancement is related to nanodiamond diameter, with enhancement increasing in the order 1000 nm < 250 nm < 100 nm < 10 nm < 5 nm. We attribute the current enhancement to two catalytic processes: i) electron transfer between the solution redox species and redox-active groups on the nanodiamond surface; ii) electron transfer mediated by FcMeOH+ adsorbed onto the nanodiamond surface. The first process is pH dependent as it depends on nanodiamond surface functionalities for which electron transfer is coupled to proton transfer. The adsorption-mediated process is observed most readily at slow scan rates and is due to self-exchange between adsorbed FcMeOH+ and FcMeOH in solution. FcMeOH+ has a strong electrostatic affinity for the nanodiamond surface, as confirmed by in situ infrared (IR) experiments.

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

2020 ◽  
Author(s):  
Andrew McNeece ◽  
Kate Jesse ◽  
Jiaze Xie ◽  
Alexander S. Filatov ◽  
John Anderson
Keyword(s):  
Redox Chemistry ◽  
Oxygen Binding ◽  
Metal Chemistry ◽  
Redox Active Ligand ◽  
Redox Couples ◽  
Redox Active ◽  
Oxidative Reactivity ◽  
Oxidative Transformations ◽  
Oxidation Chemistry ◽  
Powerful Strategy

Metal ligand cooperativity is a powerful strategy in transition metal chemistry. This type of mechanism for the activation of O<sub>2</sub> is best exemplified by heme centers in biological systems. While aerobic oxidations with Fe and Cu are well precedented, Ni-based oxidations are frequently less common due to less-accessible metal-based redox couples. Some Ni enzymes utilize special ligand environments for tuning the Ni(II)/(III) redox couple such as strongly donating thiolates in Ni superoxide dismutase. A recently characterized example of a Ni-containing protein, however, suggests an alternative strategy for mediating redox chemistry with Ni by utilizing ligand-based reducing equivalents to enable oxygen binding. While this mechanism has little synthetic precedent, we show here that Ni complexes of the redox-active ligand<i><sup> t</sup></i><sup>Bu,Tol</sup>DHP (<i><sup>t</sup></i><sup>Bu,Tol</sup>DHP = 2,5-bis((2-<i>t</i>-butylhydrazono)(<i>p</i>-tolyl)methyl)-pyrrole) activate O<sub>2</sub> to generate a Ni(II) superoxo complex via ligand-based electron transfer. This superoxo complex is competent for stoichiometric oxidation chemistry with alcohols and hydrocarbons. This work demonstrates that coupling ligand-based redox chemistry with<b> </b>functionally redox-inactive Ni centers enables oxidative transformations more commonly mediated by metals such as Fe and Cu.

scholarly journals Redox chemistry and H-atom abstraction reactivity of a terminal zirconium(iv) oxo compound mediated by an appended cobalt(i) center

2020 ◽  
Vol 11 (39) ◽  
pp. 10729-10736
Author(s):  
Hongtu Zhang ◽  
Gregory P. Hatzis ◽  
Diane A. Dickie ◽  
Curtis E. Moore ◽  
Christine M. Thomas
Keyword(s):  
Redox Chemistry ◽  
Redox Active

Bimetallic cooperativity is demonstrated with a Co/Zr complex featuring both nucleophilic Zr(iv) oxo and redox active Co sites.

scholarly journals Haem-thiolate redox enzymes: cytochrome P450 BM3 versus nitric oxide synthase: Power versus control

2003 ◽  
Vol 25 (4) ◽  
pp. 20-23
Author(s):  
Stephen K. Chapman ◽  
Simon Daff ◽  
Tobias W.B. Ost
Keyword(s):  
Nitric Oxide ◽  
Cytochrome P450 ◽  
Nitric Oxide Synthase ◽  
Redox Chemistry ◽  
Redox Enzymes ◽  
P450 Bm3 ◽  
Important Group ◽  
Redox Active ◽  
Cytochrome P450 Bm3 ◽  
Oxide Synthase

More than one-third of all enzymes catalyse the oxidation or reduction of a substrate and are therefore classed as oxidoreductases or redox enzymes. The, often complex, redox chemistry involved here is made possible by surprisingly few redox-active cofactors. Of these, flavin nucleotides (FAD and FMN) and haem groups are arguably the most significant. The P450 cytochromes (P450s) and nitric oxide synthases (NOSs) represent a very large and immensely important group of enzymes, which utilize both of these cofactors.

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

2020 ◽  
Author(s):  
Andrew McNeece ◽  
Kate Jesse ◽  
Jiaze Xie ◽  
Alexander S. Filatov ◽  
John Anderson
Keyword(s):  
Redox Chemistry ◽  
Oxygen Binding ◽  
Metal Chemistry ◽  
Redox Active Ligand ◽  
Redox Couples ◽  
Redox Active ◽  
Oxidative Reactivity ◽  
Oxidative Transformations ◽  
Oxidation Chemistry ◽  
Powerful Strategy

Metal ligand cooperativity is a powerful strategy in transition metal chemistry. This type of mechanism for the activation of O<sub>2</sub> is best exemplified by heme centers in biological systems. While aerobic oxidations with Fe and Cu are well precedented, Ni-based oxidations are frequently less common due to less-accessible metal-based redox couples. Some Ni enzymes utilize special ligand environments for tuning the Ni(II)/(III) redox couple such as strongly donating thiolates in Ni superoxide dismutase. A recently characterized example of a Ni-containing protein, however, suggests an alternative strategy for mediating redox chemistry with Ni by utilizing ligand-based reducing equivalents to enable oxygen binding. While this mechanism has little synthetic precedent, we show here that Ni complexes of the redox-active ligand<i><sup> t</sup></i><sup>Bu,Tol</sup>DHP (<i><sup>t</sup></i><sup>Bu,Tol</sup>DHP = 2,5-bis((2-<i>t</i>-butylhydrazono)(<i>p</i>-tolyl)methyl)-pyrrole) activate O<sub>2</sub> to generate a Ni(II) superoxo complex via ligand-based electron transfer. This superoxo complex is competent for stoichiometric oxidation chemistry with alcohols and hydrocarbons. This work demonstrates that coupling ligand-based redox chemistry with<b> </b>functionally redox-inactive Ni centers enables oxidative transformations more commonly mediated by metals such as Fe and Cu.

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