Probing the Mechanism and Reactivity of Biomacromolecular and Small Molecule Catalytic Systems with H2O2 and O2
Year: 2013
Type: article
Abstract: BARRIOS, DAVID ARLEN.Probing the Mechanism and Reactivity of Biomacromolecular and Small Molecule Catalytic Systems with H 2 O 2 and O 2 .(Under the direction of Dr. Reza A. Ghiladi).Dehaloperoxidase (DHP) provides both a biologically-relevant globin and peroxidase function for the marine terebellid polychaete, Amphitrite ornata.The peroxidase activity imparts a necessary detoxification pathway to combat biogenically synthesized toxins in the benthic ecosystems in habited by A. ornata.Previous studies have shown that halogenated phenols are oxidized utilizing this peroxidase mechanism.In these studies, we explore a novel peroxygenase reactivity for DHP with hydrogen peroxide in the presence a proposed native substrate, halogenated indoles.The existence of the peroxygenase pathway was confirmed using labeled oxygen studies and analysis by LC-MS.Characterization of reactive intermediates were performed using stopped-flow UV-visible spectroscopy and resonance Raman.Further, the reactivity of DHP with a non-native substrate, nitrophenol, which also exhibits peroxygenase activity, is explored using labeled oxygen studies and LC-MS as well as stopped-flow UV-visible spectroscopy.Additionally, the reactivity of DHP and H 2 O 2 with the native substrate 2,4-dichlorophenol is explored and was discovered to exhibit both peroxidase and peroxygenase activity as well as an independent dehalogenation step.Lastly, the reactivity of various iridium complexes with substituted dibenzyl ethers was explored under O 2 in dimethyl sulfoxide.
Author: David A. Barrios
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2524645441