Ferrous iron reduction of superoxide, a proton-coupled electron-transfer four-point test

The Journal of Physical Chemistry. a
Matthew C F WanderMartin A A Schoonen

Abstract

Nelsen's four-point method of separating oxidants and reductants has been tested to evaluate its applicability to proton-coupled electron-transfer reactions. An efficient computational method was developed to determine rate-limiting steps in complex, multistep redox reactions. Geochemical redox reactions are rarely single-step, and by identifying the rate-limiting steps, computational time can be greatly reduced. The reaction of superoxide and ferrous oxide was selected as a test case for its simplicity and its importance in environmental radical generation chemistry (Fenton's reaction). Two approaches, one quantum mechanical and the other semiempirical, were compared. In both approaches, hybrid density functional theory (DFT) was used with the B3LYP/6-31+G(d,p) basis set and a polarized continuum model of the solvent to minimize the structures and determine the energies. In the quantum mechanical case, DFT was used to determine both the Gibbs free energies and the values for the intrinsic component of the reorganization energy of possible combinations of reactants and products. In the latter, experimental DeltaG(f) values were combined with calculated intrinsic reorganization energy values. The computational results matched th...Continue Reading

References

Feb 6, 1999·Annual Review of Physical Chemistry·R I Cukier, D G Nocera
May 12, 2000·Chemistry : a European Journal·S F Nelsen
Oct 23, 2001·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·A M KeltererG Grampp
May 1, 2004·Annual Review of Physical Chemistry·James M Mayer
Jul 21, 2006·The Journal of Physical Chemistry. a·Ulf WahlgrenIngmar Grenthe
Aug 4, 2006·The Journal of Physical Chemistry. a·Matthew C F WanderMartin A A Schoonen
Oct 13, 2006·The Journal of Physical Chemistry. a·Stephen F NelsenJessica J O'Konek

❮ Previous
Next ❯

Citations

Nov 28, 2012·The Journal of Physical Chemistry. a·Todd F MarkleJames M Mayer
Jun 19, 2012·Chemical Reviews·David R WeinbergThomas J Meyer

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.