Coordination of mycotoxins with lanthanides in luminescent complexes

The ability of several chelating mycotoxins to form coordination complexes with the lanthanide metals europium and terbium was explored. The mycotoxins examined included ochratoxin A, citrinin, cyclopiazonic acid (CPA), kojic acid, and tenuazonic acid (TeA). Of these compounds, TeA and CPA resulted in the greatest luminescence. Parameters influencing luminescence of TeA were investigated further. These included the type of lanthanide and its concentration, certain environmental factors, and the effect of competing metal cations. Of the two lanthanide metals, the terbium coordination complex (TeA-Tb³⁺) showed greater luminescence relative to the europium complex (TeA-Eu³⁺). The effects of solvent type, water content, and pH on the TeA-Tb³⁺ system suggested that optimal conditions for luminescence were in 90% methanol with 10% aqueous buffer at pH 3. In competitive assays, the luminescence of the TeA-Tb³⁺ complex decreased as the concentration of competing metal cations increased. Among the cations tested, Cu²⁺ was the best inhibitor followed by Al³⁺, Au³⁺, Fe³⁺, Co²⁺, Mn²⁺, Mg²⁺, and Ca²⁺. Two cations, Na⁺ and K⁺, showed no significant inhibition. This is the first report to describe the coordination of the metal-chelating mycotoxin TeA with lanthanides and the ability of TeA to serve as an "antenna" for the efficient transfer of energy to the lanthanide with resulting luminescence. Understanding the ability of mycotoxins such as TeA to chelate metals provides insight into how they exert their toxic effects.