A novel chemical marker of tremorgenic mycotoxicosis detected by gas-chromatography/mass-spectrometry

Abstract

Tremorgenic mycotoxicosis can arise from dietary exposure to secondary metabolite products of various fungal species, particularly those from thePenicillium genus. Although general toxin screens often rely on gas chromatography-mass spectrometry (GC/MS) and well-developed mass spectral library databases, two principal representativePenicillium mycotoxins, roquefortine and penitrem A, are unamenable to GC/MS owing to high molecular weights, low volatilities and/or high thermal instabilities. Reliance on GC/MS screens alone could therefore inadvertently result in failure to collect evidence of exposure to such tremorgenic mycotoxins. In this report we describe a newly discovered tremorgenic marker compound (TMC), the presence of which correlates highly with conclusive exposure toPenicillium toxins in explanation of clinical manifestations of tremorgenic mycotoxicosis. According to detailed mass spectral deconvolution, the compound is 210.0892 molecular weight, and amenable to GC/MS whether chemically underivatized or derivatized by methylation or trimethylsilylation. 1D and 2D NMR (nuclear magnetic resonance) studies on the isolated compound determined the TMC to be thePenicillium product terrestric acid, C11H14O4, which matches the molecular formula determined by high resolution mass spectrometry and thus provides an excellent target for assessment of mycotoxicosis by GC/MS.