The biosynthesis of the sphinganine analogue mycotoxins (SAMs) fumonisin B1 and the AAL toxins was studied by growing Fusarium moniliforme and Alternaria alternata f. sp. lycopersici in liquid culture. Radioactive and stable isotopically labeled amino acid, water, and molecular oxygen precursors were added to the culture media and toxins were analyzed using thin-layer chromatography, liquid scintillation counting, high-performance liquid chromatography (HPLC), 13C nuclear magnetic resonance (NMR) spectroscopy, and electrospray mass spectrometry (ESMS). Results indicated that glycine was incorporated directly into the AAL toxins and that methionine was incorporated into the AAL toxin methyl groups. Oxygens in tricarballylic acid moieties for fumonisin B1 and the AAL toxins were derived from H2O while the lipid backbone hydroxyls for fumonisin B1 and the AAL toxins originated from molecular oxygen. Isotopic enrichment patterns for the various AAL toxins showed marked differences among toxins, suggesting a complex, rather than sequential, biosynthetic pattern. Keywords: Mycotoxins; sphinganine analogue mycotoxins; isotope enrichment

Diacetyl, noted for its appealing butter-like aroma, is present naturally in many foods, and humans have been exposed to it since the beginning of civilization. The advent of microwave (MW) cooking technology has led to the development of a significant market for MW popcorn, to which diacetyl and other flavoring compounds have been frequently added. Based upon reported associations between diacetyl inhalation and lung disease in employees of MW popcorn processing facilities, a very conservative safe level of occupational exposure to diacetyl has been proposed by the American Conference of Governmental Industrial Hygienists. Yet there is conflicting evidence that diacetyl causes lung disease in workers, and no evidence to condemn diacetyl as the cause of lung problems in MW popcorn consumers. Consumer dietary exposure to diacetyl in foods is below levels of health concern while common airborne levels of diacetyl from MW popcorn are far below the conservatively established limit to protect workers.

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In a series of laboratory studies, a single 4-hr acidic fog at pH levels associated with commercial celery (Apium graveolens L.) production near major population centers in California was found to stimulate development of psoralen, bergapten, xanthotoxin, and isopimpinellin within 24 hr and for at least 120 hr after exposure. At 120 hr posttreatment, the concentrations of phototoxin furanocoumarins (psoralen + bergapten + xanthotoxin) increased 540% in the leaves (to 135 μg/g fresh weight) and 440% in the petioles (to 55.56 μg/g fresh weight) of celery exposed to a pH 2.0 fog as compared to plants exposed to control fogs (pH 6.3-6.5). Concentrations of these compounds in test plants were 7.5 times higher than the amount known to produce contact dermatitis. The nonphototoxic isopimpinellin increased more than threefold in the leaves (to 39.23 μg/g fresh weight, 120 hr) and petioles (to 25.88/gmg/g fresh weight) as compared to control plants. In contrast, a single ozone fumigation at 0.20 ppm for 2 hr generally reduced concentrations of phototoxin furanocoumarin in leaves of celery within 24 hr (ozone-treated plants = 37.9, controls = 69.5 μg/g fresh weight), but levels of these chemicals in leaves of ozone-fumigated plants increased rapidly and concentrations were not significantly different at 120 hr. Isopimpinellin concentrations in foliage followed a similar trend (at 24 hr, control = 25.11, ozone treated = 10.96/gmg/g fresh weight, no difference at 120 h). In petioles, none of the linear furanocoumarin levels differed significantly at 120 hr posttreatment.

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