Aminoethylcysteine, lanthionine, cystathionine and cystine are mono-deaminated either by L-amino-acid oxidase or by a transaminase exhibiting the properties described for glutamine transaminase. The deaminated products cyclize producing the respective ketimines. Authentic samples of each ketimine were prepared by reacting the appropriate aminothiol compound with bromopyruvate, except cystine ketimine which required the interaction of thiopyruvate with cystine sulfoxide. Reduction of the first three mentioned ketimines with NaBH, yields the respective derivatives with the saturated rings of thiomorpholine and hexahydrothiazepine. The same reduction is carried out enzymically by a reductase extracted from mammalian tissues. Properties of the members of this family of compounds are described. Gas chromatography followed by mass spectrometry permits the identification of most of these products. HPLC is very useful for the determination of the ketimines by taking advantage of specific absorbance at 380 nm obtained by prior derivatization with phenylisothiocyanate. Adaptation of these and other analytical procedures to biological samples disclosed the presence of most of these compounds in bovine brain and in human urine. By using [35S]lanthionine ketimine as a representative member of the ketimine group, the specific, high-affinity, saturable and reversible binding to bovine brain membranes has been demonstrated. The binding is removed by aminoethylcysteine ketimine and by cystathionine ketimine indicating the occurrence in bovine brain of a common binding site for ketimines. The reduced ketimines are totally ineffective in competing with [35S]lanthionine ketimine. Alltogether these findings are highly indicative for the existence in mammals of a novel class of endogenous sulfur-containing cyclic products provided with a possible neurochemical function to be investigated further. Chemistry of sulfur-containing ketiminesInteraction of halopyruvate (fluoropyruvate) with aminothiols was used by Avi-Dor and Mager [l] for the quantitation of cysteine and other aminothiols by exploiting the increase of absorbance in the range of 300 nm. Hermann was the first to recognize that the typical absorbance at 296 nm of these products is due to the cyclization into a ketimine ring formed by internal addition of the amino to the carbonyl group [2, 31. In an attempt to prepare the ketimine resulting from the interaction of cysteamine with bromopyruvate [S-(2-

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Aminoethylcysteine ketimine decarboxylated dimer (simply named dimer) is a natural sulfur-containing tricyclic compound detected, until now, in human urine, bovine cerebellum, and human plasma. Recently, the antioxidant properties of this compound have been demonstrated. In this investigation, the presence of aminoethylcysteine ketimine decarboxylated dimer was identified in garlic, spinach, tomato, asparagus, aubergine, onion, pepper, and courgette. Identification of this compound in dietary vegetables was performed using gas chromatography, high-performance liquid chromatography, and gas chromatography-mass spectrometry. Results from GC analysis range in the order of 10(-4) micromol of dimer/g for all the tested vegetables. These results and the lack of a demonstrated biosynthetic pathway in humans might account for a dietary supply of this molecule.