Development and Validation of an LC-MS/MS Based Method for the Determination of Deoxynivalenol and Its Modified Forms in Maize

Abstract

The Fusarium mycotoxin deoxynivalenol (DON) is a common contaminant of cereals and is often co-occurring with its modified forms DON-3-glucoside (D3G), 3-acetyl-DON (3ADON) or 15-acetyl-DON (15ADON). A stable-isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) based method for their determination in cereals was developed and validated for maize. Therefore, 13C-labelled D3G was enzymatically produced using 13C-DON and [13C6Glc]-sucrose and used as an internal standard (IS) for D3G, while uniformly 13C labelled IS was used for the other mycotoxins. Baseline separation was achieved for the critical peak pair DON/D3G, while 3ADON/15ADON could not be fully baseline separated after testing various reversed phase, fluorinated phase and chiral LC columns. After grinding, weighing and extracting the cereal samples, the raw extract was centrifuged and a mixture of the four 13C-labelled ISs was added directly in a microinsert vial. The subsequent analytical run took 7 min, followed by negative electrospray ionization and selected reaction monitoring on a triple quadrupole MS. Maize was used as a complex cereal model matrix for validation. The use of the IS corrected the occurring matrix effects efficiently from 76 to 98% for D3G, from 86 to 103% for DON, from 68 to 100% for 15ADON and from 63 to 96% for 3ADON.

Isolation of the Main Pathogens Causing Postharvest Disease in Fresh Angelica sinensis during Different Storage Stages and Impacts of Ozone Treatment on Disease Development and Mycotoxin Production

“…F. solani can metabolize and produce trichothecene, 15-ADON, as one kind of type B trichothecene, was detected in A. sinensis fusarium rot lesions caused by F. solani . 15-ADON has various toxic effects, including anorexia, growth retardation, immunotoxicity, and impaired reproduction [ 40 ], posing a serious threat to human health. There are previous reports of 15-ADON contamination in Fusarium species-infested wheat spikes [ 41 ] and maize [ 42 ], but no report in Chinese herbs.…”

“…Mycotoxins are secondary metabolites of pathogenic molds produced under favorable conditions, having carcinogenic, teratogenic, or mutagenic effects on human health [ 40 ]. The results in the present study showed that 2 mg L −1 ozone treatment significantly reduced the mycotoxin accumulation in diseased A. sinensis tissues, and 2 h ozone exposure was more effective than the 1 h ozone exposure.…”

Recent Advances in the Detection of Food Toxins Using Mass Spectrometry

“…The presence was detected with a stable-isotope dilution liquid chromatography–tandem mass spectrometry-based approach that relies on labeling of toxins enzymatic byproducts with 13C. The method efficiently detected D3G (76–98%), DON (86–103%), 15ADON (68–100%), and 3ADON (63–96%) . Zhang et al employed ultrahigh-performance liquid chromatography–HRMS to detect 82 mycotoxins and categorize into 8 classes by Python program developed with “Fragmentation pattern screener (FPScreener)” and nontarget screening rules.…”

“…Masked mycotoxins have been detected in extractable conjugated and nonextractable varieties (usually to unavailability of toxins in extracted samples, bound mycotoxins are not accessible for analysis and need chemical or enzymatic treatment prior detection). 238 Fiby et al 239 reported the presence of Fusarium mycotoxin like deoxynivalenol in native as well as masked form (DON-3glucoside "D3G", 3-acetyl-DON "3ADON", or 15-acetyl-DON "15ADON") in cereals. The presence was detected with a stableisotope dilution liquid chromatography−tandem mass spectrometry-based approach that relies on labeling of toxins enzymatic byproducts with 13C.…”

“…The method efficiently detected D3G (76−98%), DON (86−103%), 15ADON (68− 100%), and 3ADON (63−96%). 239 Zhang et al 240 oat flour. For the identification, oat and wheat flours were treated with amylolytic enzymes (α-amylase and amyloglucosidase), similar to the one used in the cereal-based baby food production process that reduced the β-zearalenol (β-ZEL) and β-ZEL-14-sulfate by 40% within 90 min and allowed the specific detection of ZEN-sulfate derivates from cereals.…”