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LC-MS/MS acquisitions For the discovery cohort, untargeted analysis samples were analyzed by nanoLC/MSMS using a Dionex UltiMate 3000 nanoRSLC liquid chromatography system (Thermo Fisher Scientific) interfaced to an Orbitrap Fusion Tribrid mass spectrometer (Thermo Fisher Scientific, San Jose, CA,USA) equipped with a nanoelectrospray ion source