Lipids and arachidonic acid mediators; molecular redox mechanisms; magnetic resonance.

Members of the Gaffney laboratory with the lab's spectrometer.

We study the roles of unsaturated fatty acids in cells from several views. Recent studies focus on structure-function relationships of enzymes in arachidonic ac id/oxylipin cascades, including iron and manganese lipoxygenases from several species and a novel allene oxide synthase from Plexaura homomalla. Oxidatio n and reduction of metal centers are key events in the mechanisms of these enzymes. We also specialize in studying redox-active enzymes by high-, and low-freque ncy electron paramagnetic resonance (EPR). The instrumentation for the high-field studies operates at 94 GHz and is equipped for magnetic field scans from 0 to 6 Tesla. Computer simulation of EPR spectra has been developed for multielectron centers. A high frequency might be chosen in EPR studies, for example, because extremely small samples are used, magnetic-field-independent effects such as zero-field splitting become less important so resolution is improved, the contribut ions of multicomponent samples can be resolved, or a fast-motional process is involved. We aim to explore redox reactions in new enzymes as they are discovered. If you've got a favorite, let us know.