title: Determination of deoxynivalenol and deoxynivalenol-3-glucoside in wheat and barley using liquid chromatography coupled to mass spectrometry: on-line clean-up versus conventional sample preparation techniques.
abstract: In this study, we compared the performance of conventional sample preparation techniques used in mycotoxin analyses against automated on-line sample clean-up for the determination of deoxynivalenol (DON) and its conjugated derivative, deoxynivalenol-3-β-d-glucoside (D3G), in cereal grains. Blank wheat and barley samples were spiked with DON and D3G, extracted with a mixture of acetonitrile:water (84:16, v/v) and processed by one of the following: extract and shoot, MycoSep(®) 227 clean-up columns, MycoSep 227 with an additional acetonitrile elution step and centrifugal filtration, followed by analysis with liquid chromatography tandem mass spectrometry. Based on method performance characteristics and poor recoveries (<30%) obtained for the polar D3G with some techniques, the extract and shoot approach was chosen for the inter-laboratory method comparison study. Thus, the same spiked samples were analysed in parallel by another laboratory with an in-house validated on-line sample clean-up method, utilising TurboFlow™ chromatography coupled to high resolution mass spectrometry. Method validation was performed by determination of specificity, linearity, recovery, intra-day precision and the limits of detection and quantification. Matrix-matched linearity (R(2)>0.985) was established in the range of 100-1600 and 20-320μg/kg for DON and D3G, respectively. Average recoveries (%RSD) were acceptable with both methods for wheat and barley, ranging between 73% and 102% (3-12%) for DON and 72% and 98% (1-10%) for D3G. The benefit of using automated sample clean-up in comparison to extract and shoot is the ability to inject directly pure extracts into the mass spectrometer, offering faster analyses and improved sensitivity with minimum system maintenance.
authors.affiliation: Chemistry and Toxicology Unit, Finnish Food Safety Authority (Evira), Mustialankatu 3, 00790 Helsinki, Finland. Electronic address: alexis.nathanail@evira.fi.
authors.forename: Alexis V
authors.initials: AV
authors.lastname: Nathanail
authors.affiliation: Special Solutions Center, Thermo Fisher Scientific, Im Steingrund 4-6, 63303 Dreieich, Germany.
authors.forename: Ebru
authors.initials: E
authors.lastname: Sarikaya
authors.affiliation: Product Safety Unit, Finnish Food Safety Authority (Evira), Mustialankatu 3, 00790 Helsinki, Finland.
authors.forename: Marika
authors.initials: M
authors.lastname: Jestoi
authors.affiliation: Special Solutions Center, Thermo Fisher Scientific, Im Steingrund 4-6, 63303 Dreieich, Germany.
authors.forename: Michal
authors.initials: M
authors.lastname: Godula
authors.affiliation: Finnish Safety and Chemicals Agency (Tukes), Opastinsilta 12 B, 00521 Helsinki, Finland.
authors.forename: Kimmo
authors.initials: K
authors.lastname: Peltonen
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D005960:Glucosides / Q000032:analysis*; D001467:Hordeum / Q000737:chemistry*; D057230:Limit of Detection; D009183:Mycotoxins / Q000032:analysis; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014255:Trichothecenes / Q000032:analysis*; D014908:Triticum / Q000737:chemistry*
chemical_list: D005960:Glucosides; D009183:Mycotoxins; D014255:Trichothecenes; C542050:deoxynivalenol-3-glucoside; C007262:deoxynivalenol
keywords: Biologically modified mycotoxins inter-laboratory method comparison; Cereals; High resolution mass spectrometry; TurboFlow™ chromatography