Roles for glutathione transferases in plant secondary metabolism

Plant glutathione transferases (GSTs) are classified as enzymes of secondary metabolism, but while their roles in catalysing the conjugation and detoxification of herbicides are well known, their endogenous functions are largely obscure Thus, while the presence of CST-derived S-glutathionylated xenobiotics have been described in many plants, there is little direct evidence for the accumulation of similarly conjugated natural products, despite the presence of a complex and dichotomous metabolic pathway which processes these reaction products The conservation in glutathione Conjugating and processing pathways, the co-regulation of GSTs with inducible plant secondary metabolism and biochemical studies showing the potential of these enzymes to conjugate reactive natural products are all suggestive of important endogenous functions As a framework for addressing these enigmatic functions we postulate that either (a) the natural reaction products of GSTs are unstable and undergo reversible S-glutathionylation, (b) the conjugation products of GSTs are very rapidly processed to derived metabolites, (c) GSTs do not catalyse conventional conjugation reactions but instead use glutathione as a cofactor rather than co-substrate, or (d) GSTs are non-catalytic and function as transporter proteins for secondary metabolites and their unstable intermediates. In this review, we describe how enzyme biochemistry and informatics are providing clues as to CST function allowing for the critical evaluation of each of these hypotheses We also present evidence for the involvement of GSTs in the synthesis of sulfur-containing secondary metabolites such as volatiles and glucosincilates, and the conjugation, transport and storage of reactive oxylipins, phenolics and flavonoids. (C) 2010 Elsevier Ltd All rights reserved