Keith P. Madden Cornell University, B.A. ('74) University of Rochester, M.S. ('77) Ph.D. ('80) Tel. (574) 631-7279 e-mail: madden.1@nd.edu Kinetics and Mechanism of Spin Trapping Reactions

Scientific Interests

Design — and implementation of computer-based systems for the evaluation and dissemination of chemical property data, particularly the kinetics of radiation-induced transients in condensed media.

Quantitative studies of spin trapping — nitrones and nitroso compounds.

Free-radical chemistry — carbohydrates and model systems in aqueous solution.

ESR instrumentation — development of time-resolved electron spin resonance spectroscopy instrumentation and methodology.

Recent Accomplishments | Top |

Completion of the RCDC compilation — "Critical Review of Rate Constants for Reactions of Hydrogen Atoms in Aqueous Solution" covering the period 1988-2007.

Spin trapping of water radicals — The definitive determination of the rate constant for the reaction of hydroxyl radical and hydrated electron with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and the direct measurement of the yield of DMPO-OH spin adduct were accomplished using direct-detection TRESR.

Alkyl radicals in aqueous solutions — We performed the first direct ESR measurement of the rate constant and activation energy for the recombination of methyl radicals in aqueous solution.

Selected Publications | Top |

S.P. Mezyk, D.B. Ewing, J.J. Kiddle and K.P. Madden
Kinetics and mechanisms of the reactions of hydroxyl radicals and hydrated electrons with nitrosamines and nitramines in water
J. Phys. Chem. A 2006 110, 4732-7 link

S.P. Mezyk, W.J. Cooper, K.P. Madden and D.M. Bartels
Free radical destruction of N-nitrosodimethylamine in water
Environ. Sci. Technol. 2004 38, 3161-7 link

K.P. Madden and H. Taniguchi
The role of the DMPO-hydrated electron spin adduct in DMPO-·OH spin trapping
Free Radicals Biol. Med. 2001 30, 1374-80 link

H. Taniguchi and K.P. Madden
DMPO-alkyl radical spin trapping: an in situ radiolysis steady-state ESR study
Radiat. Res. 2000 153, 447-53 link

H. Taniguchi and K.P. Madden
An in situ radiolysis time-resolved ESR study of the kinetics of spin trapping by 5,5-dimethyl-1-pyrroline-N-oxide
J. Am. Chem. Soc. 1999 121, 11875-9 link

Supported by the Division of
Chemical Sciences
Office of
Basic Energy Sciences
at the
U.S. Department of Energy

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Last Modified: 05/03/2008