The great research interest in the quantification of reactive carbonyl compounds (RCCs), such as methylglyoxal (MGO) in biological and environmental samples, is reflected by the fact that several publications have described specific strategies to perform this task. Thus, many reagents have also been reported for the derivatization of RCCs to effectively detect and quantify the resulting compounds using sensitive techniques such as liquid chromatography coupled with mass spectrometry (LC-MS). However, the choice of the derivatization protocol is not always clear, and a comparative evaluation is not feasible because detection limits from separate reports and determined with different instruments are hardly comparable. Consequently, for a systematic comparison, we tested 21 agents in one experimental setup for derivatization of RCCs prior to LC-MS analysis. This consisted of seven commonly employed reagents and 14 similar reagents, three of which were designed and synthesized by us. All reagents were probed for analytical responsiveness of the derivatives and stability of the reaction mixtures. The results showed that derivatives of 4-methoxyphenylenediamine and 3-methoxyphenylhydrazine-reported here for the first time for derivatization of RCCs-provided a particularly high responsiveness with ESI-MS detection. We applied the protocol to investigate MGO contamination of laboratory water and show successful quantification in a lipoxidation experiment. In summary, our results provide valuable information for scientists in establishing accurate analysis of RCCs.

Department of Bioorganic Chemistry Leibniz Institute of Plant Biochemistry 06120 Halle Germany

Institute of Analytical Chemistry Faculty of Chemistry and Mineralogy University of Leipzig 04103 Leipzig Germany

Institute of Analytical Chemistry Faculty of Chemistry and Mineralogy University of Leipzig 04103 Leipzig Germany Department of Chemistry Krishna University Machilipatnam 521001 Andhra Pradesh India

Institute of Analytical Chemistry Faculty of Chemistry and Mineralogy University of Leipzig 04103 Leipzig Germany Department of Plant Physiology and Biochemistry Faculty of Biology Saint Petersburg State University Saint Petersburg 199034 Russia Library of the Russian Academy of Sciences Saint Petersburg 199034 Russia

Institute of Analytical Chemistry Faculty of Chemistry and Mineralogy University of Leipzig 04103 Leipzig Germany Faculty of Tropical AgriSciences Czech University of Life Sciences Prague 165 00 Prague Suchdol Czech Republic

Institute of Analytical Chemistry Faculty of Chemistry and Mineralogy University of Leipzig 04103 Leipzig Germany Institute of Pharmacy Faculty of Medicine University of Leipzig 04103 Leipzig Germany

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