Gardner H W. Decomposition of linoleic acid hydroperoxides. Enzymic reactions compared with nonenzymic. J. Agr. Food Chem. 23: 129-36. 1975

Following research assignments in Hawaii and California, I accepted a position at the Northern Regional Research Center in Peoria (from whence all roads lead to soybean and cornfields), in order to reduce unnecessary but tempting distractions. My time, in those early US Department of Agriculture years, was divided between mission-oriented work and maverick research on the chemistry and biochemistry of lipid hydroperoxides. Attendance at a symposium on the latter topic resulted in an invitation to write this review, of which I now share some personal thoughts. The citation rate of this article, and that of another highly cited paper of mine appearing in the same journal, 1 illustrate the impact of timely ournal-psablished reviews. By comparison, my book chapters have been condemned to near oblivion. Personal research into previously unknown reactions of lipid hydroperoxides furnished recency to the review. For example, investigation of an iron-catalyzed redox reaction between cysteine and linoleic acid hydroperoxide suggested a novel pathway to isomeric epoxyhydroxy and epoxyoxo fatty acids. The mechanism, an intramolecular rearrangement of an alkoxyl radical into an epoxyallylic radical, was incorporated into a research manuscript that reported the work, but it was promptly rejected by a well-meaning reviewer who objected to a figure showing the postulate. And so, via this review, the contested mechanism found its way into print anyway. Dogged persistence is sometimes necessary to overcome entrenched resistance,but it is not always without hazard. Certain structural features of products from the iron-catalyzed reaction were similar to those of products isolated from a reaction ofsoybean lipoxygenase under anaerobic conditions. Since lipoxygenase contains iron at the active site, it seemed a good bet that the enzyme mechanism might be similar to that of the nonenzymatic reaction. My proposal for the aerobic and anaerobic mechanisms of lipoxygenase was nearly identical to the model eventually adopted. However, my review has rarely, if ever, been cited specifically regarding the lipoxygenase proposal, because preeminent lipoxygenase investigators simultaneously published their own mechanism. 2