Various filamentous fungi can produce secondary metabolites, whose biochemical significance in fungal growth and development has not always been fully clarified; however, some of these metabolites can cause deleterious effects on other organisms and are classified as mycotoxins [...]

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Toxins

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Various filamentous fungi can produce secondary metabolites, whose biochemical significance in fungal growth and development has not always been fully clarified; however, some of these metabolites can cause deleterious effects on other organisms and are classified as mycotoxins [...

Aldo Laganà

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Introduction to the Toxins Special Issue on LC-MS/MS Methods for Mycotoxin Analysis

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Archivio della ricerca- Università di Roma La Sapienza

toxinsEditorialIntroduction to the Toxins Special Issue onLC-MS/MSMethods for Mycotoxin AnalysisAldo Laganà IDDepartment of Chemistry, Università di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy;aldo.lagana@uniroma1.it; Tel.: +39-06-4991-3679Academic Editor: Sarah De SaegerReceived: 30 August 2017; Accepted: 10 October 2017; Published: 16 October 2017Various filamentous fungi can produce secondary metabolites, whose biochemical significancein fungal growth and development has not always been fully clarified; however, some of thesemetabolites can cause deleterious effects on other organisms and are classified as mycotoxins. The mainmycotoxin-producing fungi belong to species of Fusarium, Aspergillus, Penicillium, Claviceps andAlternaria genera. Mostly, human exposure to mycotoxins occurs through the intake of contaminatedagricultural products, or indirectly through the intake of residues or metabolite products present infoods of animal origin. Seldom, exposure may also occur through dermal contact and inhalation.The known mycotoxins belong to heterogeneous chemical classes, and they can exert highly diversetoxic effects (e.g., cancerogenic and immunosuppressive effects).Immunochemical methods (such as ELISA) can be used for rapid screening of mycotoxinpresence; however, for confirmation purposes, analytical methods based on high-performanceliquid chromatography (LC) are preferred, especially when coupled with tandem mass spectrometry(MS/MS), which allows the determination of multiclass mycotoxins in a single analysis. Moreover,the technical innovations available in LC-MS/MS instrumentation are prompting its application inmonitoring the presence of contaminants in food and feed. The aim of this Special Issue is to explorethe capabilities of LC-MS/MS methods in mycotoxin investigation.The topic of LC-MS/MS multi-mycotoxin determination is addressed in most papers. Indeed,as reported by De Santis et al. [1], due to the actual probability that co-occurring mycotoxins arepresent in a food or feed product, nowadays, the availability of reliable, sensitive, and versatilemulti-mycotoxin methods is increasingly important; moreover, there is a wide range of matricessusceptible to mycotoxin contamination. For these reasons, the authors validated a multi-mycotoxinand multi-matrix LC-MS/MS-based method of overcoming specific matrix effects (no sample clean-upwas performed after acetonitrile-water extraction) and analyzing complex cereal-based samples.The investigated mycotoxins were aflatoxin B1 (AFB1), ochratoxin A (OTA), deoxynivalenol (DON),fumonisin B1 (FB1), zearalenone (ZEN), T-2 and HT-2 toxins.In this special issue, Kim et al. [2] proposed an LC-MS/MS method for the simultaneousdetermination of 13 mycotoxins, namely DON, nivalenol (NIV), 3-acetylnivalenol, the main fouraflatoxins (AFB1, AFB2, AFG1, and AFG2), FB1, fumonisin B2 (FB2), T-2, HT-2, ZEN, and OTA,in cereal grains. After the classical acetonitrile-water mixture extraction step, the sample was cleanedup by a single immunoaffinity column. In the survey of samples from South Korea, DON, NIV andZEN were more frequently and concurrently detected in all cereal grains than OTA and AFs.To make mycotoxin analysis more environmentally friendly, Breidbach [3] extracted DON, T-2,HT-2, and ZEN by replacing acetonitrile by ethyl acetate, and forgoing sample extract clean-up,thus minimizing solvent consumption. The LC-MS/MS method was validated in-house and througha collaborative study. The extraction was also adapted to a quick screening of AFB1 in maizeby flow-injection—MS.Toxins 2017, 9, 325; doi:10.3390/toxins9100325 www.mdpi.com/journal/toxinsToxins 2017, 9, 325 2 of 3A method based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) purificationfollowed by LC-MS/MS analysis was optimized by Sun et al. [4] for the simultaneous quantificationof 25 mycotoxins in cereals. In this case, aside from the classically investigated mycotoxins,sterigmatocystin (STC), verruculogen, enniatins, beauvericin, gliotoxin and other were also included.Eight laboratories performed an interlaboratory study to validate an LC-MS/MS method forthe simultaneous determination of AFs and STC in white rice and sorghum [5]. Sample purificationwas carried out by solid-phase extraction. The validated method was successfully applied for thedetermination of AFs and STC in 20 white rice and 20 sorghum samples collected from Korean markets.Mycotoxins can undergo modification in plants, leading to the formation of a large numberof possible modified forms, whose toxicological relevance and occurrence in food and feed is stilllargely unexplored. The analysis of modified mycotoxins by LC-MS remains a challenge becauseof their chemical diversity, the large number of isomeric forms, and the lack of analytical standards.Therefore, Righetti et al. [6] explored and reviewed the potential benefits of high-resolution (HR) andion mobility MS as a tool for separation and structure confirmation of modified mycotoxins. In fact,the analytical potential of high resolving power, accurate mass, and acquisition in full scan permits aretrospective analysis using extensive databases of hundreds of analytes and enabling the investigationof ‘newly discovered’ mycotoxins in the data of previously-analyzed samples. However, applicationsof ion mobility spectrometry in the separation and structure confirmation of mycotoxins have not beenexplored adequately so far, even though it offers great potential for gaining insight into the formationand characterization of new modified forms.The use of 13C-assisted LC-HRMS for the first comprehensive study on the biotransformationof HT-2 and T2- in oats is described by Meng-Reiterer et al. [7]. Using this approach, 16 HT-2 and17 T-2 metabolites were annotated, including novel glycosylated and hydroxylated forms of the toxins,hydrolysis products, and conjugates with acetic acid, putative malic acid, malonic acid, and ferulic acid.Further targeted quantitative analysis was performed to study toxin metabolism over time, as well astoxin and conjugate mobility within non-treated plant tissues. The results show that the combinationof untargeted and targeted analysis is well suited to the comprehensive elucidation of mycotoxinmetabolism in plants.In this Special Issue, a survey on a very large sample set is also included. More than 1900 sampleswere analyzed for toxins and metabolites by Kovalsky et al. [8], and up to 68 metabolites were found ina single sample. Co-occurrence of regulated toxins was frequent with e.g., enniatins, and moniliformin.Results indicate that considerably more than 25% of agricultural commodities could be contaminatedwith mycotoxins, as suggested by FAO, although this is at least partly due to the lower limits ofdetection in the current survey. Observed contamination ranged from 7 to 79% for B trichothecenesand 88% for ZEN.Alternaria toxins (ATs) are usually less frequently studied; nevertheless, some papers about themare also presented in this collection. The formation of ATs depends on the species and complexinteractions of various environmental factors, and is not fully understood. Therefore, Zwickel et al. [9]studied the influence of temperature, substrate, and incubation time on the production of thirteen ATsand three sulfoconjugated ATs by three different Alternaria isolates.Rodríguez-Carrasco et al. [10] developed an analytical method based on LC-MS/MS detectionfor the simultaneous quantification of the three main ATs in tomato and tomato-based products.The extraction was performed by dispersive liquid-liquid microextraction (DLLME). Mycotoxins wereefficiently extracted from sample into a droplet of chloroform by DLLME technique using acetonitrileas a disperser solvent.The possible exposure to four ATs from grain and grain-based products has been studied byXu et al. [11]. A total of 370 freshly harvested wheat kernel samples collected in China were analyzed.I hope that this Special Issue, constituted by ten research articles and one review, will providereaders an overview about the multi-mycotoxin analysis and new insights on the investigation ofToxins 2017, 9, 325 3 of 3emerging and modified mycotoxins. In particular, the identification of modified mycotoxins andmycotoxin metabolites could take advantage of the unique identification features of HR MS.References1. De Santis, B.; Debegnach, F.; Gregori, E.; Russo, S.; Marchegiani, F.; Moracci, G.; Brera, C. Development of aLC-MS/MS Method for the Multi-Mycotoxin Determination in Composite Cereal-Based Samples. Toxins2017, 9, 169. [CrossRef] [PubMed]2. Kim, D.-H.; Hong, S.-Y.; Kang, J.; Cho, S.; Lee, K.; An, T.; Lee, C.; Chung, S. Simultaneous Determinationof Multi-Mycotoxins in Cereal Grains Collected from South Korea by LC/MS/MS. Toxins 2017, 9, 106.[CrossRef] [PubMed]3. Breidbach, A. A Greener, Quick and Comprehensive Extraction Approach for LC-MS of Multiple Mycotoxins.Toxins 2017, 9, 91. [CrossRef] [PubMed]4. Sun, J.; Li, W.; Zhang, Y.; Hu, X.; Wu, L.; Wang, B. QuEChERS Purification Combined with Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry for Simultaneous Quantification of25 Mycotoxins in Cereals. Toxins 2016, 8, 375. [CrossRef] [PubMed]5. Ok, H.; Tian, F.; Hong, E.; Paek, O.; Kim, S.-H.; Kim, D.; Chun, H. Harmonized Collaborative Validationof Aflatoxins and Sterigmatocystin in White Rice and Sorghum by Liquid Chromatography Coupled toTandem Mass Spectrometry. Toxins 2016, 8, 371. [CrossRef] [PubMed]6. Righetti, L.; Paglia, G.; Galaverna, G.; Dall’Asta, C. Recent Advances and Future Challenges in ModifiedMycotoxin Analysis: Why HRMS Has Become a Key Instrument in Food Contaminant Research. Toxins 2016,8, 361. [CrossRef] [PubMed]7. Meng-Reiterer, J.; Bueschl, C.; Rechthaler, J.; Berthiller, F.; Lemmens, M.; Schuhmacher, R. Metabolism ofHT-2 Toxin and T-2 Toxin in Oats. Toxins 2016, 8, 364. [CrossRef] [PubMed]8. Kovalsky, P.; Kos, G.; Nährer, K.; Schwab, C.; Jenkins, T.; Schatzmayr, G.; Sulyok, M.; Krska, R. Co-Occurrenceof Regulated, Masked and Emerging Mycotoxins and Secondary Metabolites in Finished Feed andMaize—An Extensive Survey. Toxins 2016, 8, 363. [CrossRef] [PubMed]9. Zwickel, T.; Kahl, S.; Klaffke, H.; Rychlik, M.; Müller, M. Spotlight on the Underdogs—An Analysis ofUnderrepresented Alternaria Mycotoxins Formed Depending on Varying Substrate, Time and TemperatureConditions. Toxins 2016, 8, 344. [CrossRef] [PubMed]10. Rodríguez-Carrasco, Y.; Mañes, J.; Berrada, H.; Juan, C. Development and Validation of a LC-ESI-MS/MSMethod for the Determination of Alternaria Toxins Alternariol, Alternariol Methyl-Ether and Tentoxin inTomato and Tomato-Based Products. Toxins 2016, 8, 328. [CrossRef] [PubMed]11. Xu, W.; Han, X.; Li, F.; Zhang, L. Natural Occurrence of Alternaria Toxins in the 2015 Wheat from AnhuiProvince, China. Toxins 2016, 8, 308. [CrossRef] [PubMed]© 2017 by the author. Licensee MDPI, Basel, Switzerland. This article is an open accessarticle distributed under the terms and conditions of the Creative Commons Attribution(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Introduction to the toxins special issue on LC-MS/MS methods for mycotoxin analysis

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