EPR detection of Fe(V)=O active species in nonheme iron-catalyzed oxidations

2012 ◽  
Vol 29 ◽  
pp. 105-108 ◽  
Author(s):  
Oleg Y. Lyakin ◽  
Irene Prat ◽  
Konstantin P. Bryliakov ◽  
Miquel Costas ◽  
Evgenii P. Talsi
Keyword(s):  
Active Species ◽  
Nonheme Iron

ChemInform Abstract: Active Species of Nonheme Iron and Manganese-Catalyzed Oxidations

ChemInform ◽  
2013 ◽  
Vol 44 (37) ◽  
pp. no-no
Author(s):  
Oleg Y. Lyakin ◽  
Roman V. Ottenbacher ◽  
Konstantin P. Bryliakov ◽  
Evgenii P. Talsi
Keyword(s):  
Active Species ◽  
Nonheme Iron ◽  
Iron And Manganese

scholarly journals A Comparative Review on the Catalytic Mechanism of Nonheme Iron Hydroxylases and Halogenases

Catalysts ◽  
2018 ◽  
Vol 8 (8) ◽  
pp. 314 ◽  
Author(s):  
Amy Timmins ◽  
Sam P. de Visser
Keyword(s):  
Hydrogen Peroxide ◽  
Molecular Oxygen ◽  
Catalytic Mechanism ◽  
Computational Modelling ◽  
Active Species ◽  
Nonheme Iron ◽  
Comparative Review ◽  
Modelling Studies ◽  
Iron Heme ◽  
And Function

Enzymatic halogenation and haloperoxidation are unusual processes in biology; however, a range of halogenases and haloperoxidases exist that are able to transfer an aliphatic or aromatic C–H bond into C–Cl/C–Br. Haloperoxidases utilize hydrogen peroxide, and in a reaction with halides (Cl−/Br−), they react to form hypohalides (OCl−/OBr−) that subsequently react with substrate by halide transfer. There are three types of haloperoxidases, namely the iron-heme, nonheme vanadium, and flavin-dependent haloperoxidases that are reviewed here. In addition, there are the nonheme iron halogenases that show structural and functional similarity to the nonheme iron hydroxylases and form an iron(IV)-oxo active species from a reaction of molecular oxygen with α-ketoglutarate on an iron(II) center. They subsequently transfer a halide (Cl−/Br−) to an aliphatic C–H bond. We review the mechanism and function of nonheme iron halogenases and hydroxylases and show recent computational modelling studies of our group on the hectochlorin biosynthesis enzyme and prolyl-4-hydroxylase as examples of nonheme iron halogenases and hydroxylases. These studies have established the catalytic mechanism of these enzymes and show the importance of substrate and oxidant positioning on the stereo-, chemo- and regioselectivity of the reaction that takes place.

EPR Spectroscopic Trapping of the Active Species of Nonheme Iron-Catalyzed Oxidation

2009 ◽  
Vol 131 (31) ◽  
pp. 10798-10799 ◽  
Author(s):  
Oleg Y. Lyakin ◽  
Konstantin P. Bryliakov ◽  
George J. P. Britovsek ◽  
Evgenii P. Talsi
Keyword(s):  
Active Species ◽  
Nonheme Iron ◽  
Catalyzed Oxidation

scholarly journals Density Functional Theory Study into the Reaction Mechanism of Isonitrile Biosynthesis by the Nonheme Iron Enzyme ScoE

2021 ◽  
Author(s):  
Hafiz Saqib Ali ◽  
Sidra Ghafoor ◽  
Sam P. de Visser
Keyword(s):  
Reaction Mechanism ◽  
Hydrogen Atom ◽  
Proton Transfer ◽  
Active Site ◽  
Density Functional ◽  
Active Species ◽  
Nonheme Iron ◽  
Catalytic Cycle ◽  
Hydrogen Atom Abstraction ◽  
Catalytic Cycles

AbstractThe nonheme iron enzyme ScoE catalyzes the biosynthesis of an isonitrile substituent in a peptide chain. To understand details of the reaction mechanism we created a large active site cluster model of 212 atoms that contains substrate, the active oxidant and the first- and second-coordination sphere of the protein and solvent. Several possible reaction mechanisms were tested and it is shown that isonitrile can only be formed through two consecutive catalytic cycles that both use one molecule of dioxygen and α-ketoglutarate. In both cycles the active species is an iron(IV)-oxo species that in the first reaction cycle reacts through two consecutive hydrogen atom abstraction steps: first from the N–H group and thereafter from the C–H group to desaturate the NH-CH2 bond. The alternative ordering of hydrogen atom abstraction steps was also tested but found to be higher in energy. Moreover, the electronic configurations along that pathway implicate an initial hydride transfer followed by proton transfer. We highlight an active site Lys residue that is shown to donate charge in the transition states and influences the relative barrier heights and bifurcation pathways. A second catalytic cycle of the reaction of iron(IV)-oxo with desaturated substrate starts with hydrogen atom abstraction followed by decarboxylation to give isonitrile directly. The catalytic cycle is completed with a proton transfer to iron(II)-hydroxo to generate the iron(II)-water resting state. The work is compared with experimental observation and previous computational studies on this system and put in a larger perspective of nonheme iron chemistry.

Active Species of Nonheme Iron and Manganese-Catalyzed Oxidations

2013 ◽  
Vol 56 (11) ◽  
pp. 939-949 ◽  
Author(s):  
Oleg Y. Lyakin ◽  
Roman V. Ottenbacher ◽  
Konstantin P. Bryliakov ◽  
Evgenii P. Talsi
Keyword(s):  
Active Species ◽  
Nonheme Iron ◽  
Iron And Manganese

Invasive species in the flora of Ukraine. I. The group of highly active species

Geo&Bio ◽  
2019 ◽  
Vol 2019 (17) ◽  
pp. 116-135 ◽  
Author(s):  
Vira V. Protopopova ◽  
◽  
Myroslav Shevera
Keyword(s):  
Invasive Species ◽  
Active Species ◽  
Highly Active

Studies on Cerium Electrochemistry in High Temperature Ionic Liquids

2018 ◽  
Vol 69 (1) ◽  
pp. 112-115
Author(s):  
Ana Maria Popescu ◽  
Virgil Constantin
Keyword(s):  
Molten Salts ◽  
Electrochemical Techniques ◽  
Active Species ◽  
Single Step ◽  
Cathodic Process ◽  
Molybdenum Electrode ◽  
Solute Interaction ◽  
Ohmic Drop ◽  
State Potential ◽  
Direct Discharge

The cathodic behavior of Ce3+ ions in LiF-NaF-BaF2, LiF-NaF-NaCl and NaCl-KCl molten salts at 730� C has been studied using different electrochemical techniques. The decomposition potential (Ed) and the cathodic overvoltage were determined by introducing NaCeF4 as electrochemical active species using steady-state potential-current curves recorded under galvanostatic conditions. The values of |Ed| were 1.85 V in LiF-NaF-BaF2, 2.114 V in LiF-NaF-NaCl and 2.538 V in NaCl-KCl, respectively. It was also found that the ohmic drop potential in melt is not dependent on NaCeF4 concentration and it rises as the current intensity increases. The Tafel slopes and other kinetic parameters were calculated on the assumption that the cathodic process consisted of direct discharge of Ce3+, with no solvent-solute interaction. In order to elucidate the mechanisn of cathodic process the cyclic voltammetry technique was finally used. From the evolution of the voltammograms we conclude that the electrochemical reduction of Ce3+ ion is actually a reversible process on the molybdenum electrode and cathodic reduction of Ce3+ takes place in one single step involving three electron exchange. Our study adds to the accumulating data and confirms available results of electrodeposition of metalic cerium from molten salts using NaCeF4 as solute.

Sewage sludge as a precursor of adsorbents/catalysts for environmental applications

2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  
Keyword(s):  
Sewage Sludge ◽  
Room Temperature ◽  
Waste Water Treatment ◽  
Textural Properties ◽  
Active Species ◽  
Elemental Sulphur ◽  
Gaseous Emissions ◽  
Removal Experiments ◽  
Catalytically Active

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.

Enhancement of hydroxyl radical generation by phenols and their reaction intermediates during ozonation

1998 ◽  
Vol 38 (6) ◽  
pp. 147-154 ◽  
Author(s):  
Hideo Utsumi ◽  
Sang-Kuk Han ◽  
Kazuhiro Ichikawa
Keyword(s):  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Spin Trapping ◽  
Active Species ◽  
Generation Rate ◽  
Peak Height Ratio ◽  
Dependent Manner ◽  
Concentration Dependent Manner ◽  
Phenol Derivatives ◽  
Semiquinone Radicals

Generation of hydroxyl radicals, one of the major active species in ozonation of water was directly observed with a spin-trapping/electron spin resonance (ESR) technique using 5,5-dimethyl-1-pyrrolineN-oxide (DMPO) as a spin-trapping reagent. Hydroxyl radical were trapped with DMPO as a stable radical, DMPO-OH. Eighty μM of ozone produced 1.08 X 10-6M of DMPO-OH, indicating that 1.4% of •OH is trapped with DMPO. Generation rate of DMPO-OH was determined by ESR/stopped-flow measurement. Phenol derivatives increased the amount and generation rate of DMPO-OH, indicating that phenol derivatives enhance •OH generation during ozonation of water. Ozonation of 2,3-, 2,5-, 2,6-dichlorophenol gave an ESR spectra of triplet lines whose peak height ratio were 1:2:1. ESR parameters of the triplet lines agreed with those of the corresponding dichloro-psemiquinone radical. Ozonation of 2,4,5- and 2,4,6-trichlorophenol gave the same spectra as those of 2,5- and 2,6-dichlorophenol, respectively, indicating that a chlorine group in p-position is substituted with a hydroxy group during ozonation. Amounts of the radical increased in an ozone-concentration dependent manner and were inhibited by addition of hydroxyl radical scavengers. These results suggest that p-semiquinone radicals are generated from the chlorophenols by hydroxyl radicals during ozonation. The p-semiquinone radicals were at least partly responsible for enhancements of DMPO-OH generation.

Sign in / Sign up

Export Citation Format

Share Document