Membrane filters

Cis-4,7,10,13,16,19-Docosahexanoic acid (DHA) and apigenin were purchased from Carbosynth Ltd. Formic acid (98%, LC-MS grade) was obtained from Fluka. Methanol, water, LC-MS grade, as well as N, N’-dicyclohexylcarbodiimide (DCC), dimethylaminopyridine (DMAP), Methanol, dichloromethane, acetonitrile, HPLC grade all, and trifluoroacetic acid (peptide synthesis grade) were obtained from Fisher Scientific. TLC of the highest available purity was carried out on silica gel plates (UV254) obtained from Alfa Aesar. DMSO (LC-MS grade) was purchased from Thermo Scientific. DMSO-d₆ (99.8%) was purchased from Euriso-top. NMR experiments were performed on a Bruker Avance 400 MHz spectrometer equipped with a z-gradient unit (Bruker BioSpin, Rheinstetten, Germany). Membrane filters with a 0.2 μm pore size and a 4 mm diameter were purchased from Phenomenex. High purity argon was used as a collision gas. ADP was obtained from Chrono-Log Corp (Havertown, PA, USA). AA was purchased from Sigma-Aldrich, St. Louis, MO, USA, and TRAP-6 was obtained from Bachem, Bubendorf, Switzerland. For the stability studies, drug-free human plasma from healthy donors was kindly offered from the Blood Donation Center of the University Hospital of Ioannina.

Dimethomorph, mandipropamid, myclobutanil, and metalaxyl were purchased from Kemidas Co. (Suwon, Republic of Korea). The chemical structures and physicochemical properties of the four pesticides are presented in Supplementary Material Table S1. Formulations of dimethomorph (wettable powder (WP), 25%, Dongbang Agro Corporation, Seoul, Republic of Korea), mandipropamid (suspension concentrate, 22.59%, Syngenta Korea Ltd., Jeonbuk, Republic of Korea), myclobutanil (WP, 6%, Kyung Nong Corporation, Seoul, Republic of Korea), and metalaxyl (WP, 25%, Enbio Co., Ltd., Gunpo-si, Republic of Korea) used in greenhouse experiments were purchased from a local market (Seoul, the ROK). HPLC-grade acetonitrile was provided by J. T. Baker (Phillipsburg, NJ, USA). Formic acid (>98% purity) was obtained from Merck KGaA (Darmstadt, Germany). Membrane filters (0.2 µm) were purchased from Phenomenex (Torrance, CA, USA). An EN-QuEChERS kit was purchased from Chiral Technology Korea (Daejeon, Republic of Korea).