title: Molecular formula analysis of fragment ions by isotope-selective collision-induced dissociation tandem mass spectrometry of pharmacologically active compounds.
abstract: The purpose of this work is to explore the mass fragment characterization of commonly used drugs through a novel approach, which involves isotope-selective tandem mass spectrometry (MS/MS). Collision-induced dissociation (CID) was performed with a low-resolution linear ion trap mass spectrometer in positive electrospray ionization. Three pharmacologically active ingredients, i.e. omeprazole, meloxicam and brinzolamide, selected as model compounds in their own formulation, were investigated as a sodiated adduct [C17 H19 N3 O3 S + Na](+) (omeprazole) and as protonated adducts, [C14 H13 N3 O4 S2  + H](+) and [C12 H21 N3 O5 S3  + H](+) , meloxicam and brinzolamide, respectively. Selecting a narrow window of ±0.5 m/z units, precursor ion fragmentation by CID-MS/MS of isotopologues A + 0, A + 1 and A + 2 was found very useful to confirm the chemical formula of product ions, thus aiding the establishment of characteristic fragmentation pathways of all three examined compounds. The correctness of putative molecular formula of product ions was easily demonstrated by exploiting the isotope peak abundance ratios (i.e. IF+0 /IF+1 and IF+0 /IF+2 ) as simple constraints in low-resolution MS instrumentations.
authors.affiliation: Dipartimento di Scienze, Università della Basilicata, Via dell'Ateneo Lucano 10, 85100, Potenza, Italy.
authors.forename: Giuliana
authors.initials: G
authors.lastname: Bianco
authors.forename: Alessandro
authors.initials: A
authors.lastname: Buchicchio
authors.forename: Filomena
authors.initials: F
authors.lastname: Lelario
authors.forename: Tommaso R I
authors.initials: TR
authors.lastname: Cataldi
mesh_terms: D000894:Anti-Inflammatory Agents, Non-Steroidal / Q000737:chemistry; D000897:Anti-Ulcer Agents / Q000737:chemistry; D002257:Carbonic Anhydrase Inhibitors / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D007554:Isotopes / Q000737:chemistry; D000077239:Meloxicam; D009853:Omeprazole / Q000737:chemistry; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013449:Sulfonamides / Q000737:chemistry; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013843:Thiazines / Q000737:chemistry; D013844:Thiazoles / Q000737:chemistry
chemical_list: D000894:Anti-Inflammatory Agents, Non-Steroidal; D000897:Anti-Ulcer Agents; D002257:Carbonic Anhydrase Inhibitors; D007477:Ions; D007554:Isotopes; D011522:Protons; D013449:Sulfonamides; D013843:Thiazines; D013844:Thiazoles; C111827:brinzolamide; D009853:Omeprazole; D000077239:Meloxicam
keywords: CID-MS/MS; elemental composition; isotopologues; linear ion trap mass spectrometry; pharmacologically active compounds