title: Binary fluorous alkylation of biogenic primary amines with perfluorinated aldehyde followed by fluorous liquid chromatography-tandem mass spectrometry analysis.
abstract: We have developed a novel method for the determination of biogenic amines (dopamine, norepinephrine, 3-methoxytyramine, normetanephrine, serotonin, tyramine, tryptamine, 5-methoxytryptamine, and histamine) utilizing liquid chromatography with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) combined with a separation-oriented derivatization technique. Using this approach, primary amino groups in the target amines were selectively dialkylated with a perfluorinated aldehyde reagent (2H,2H,3H,3H-perfluoroundecan-1-al) through reductive amination. The derivatives were directly injected onto an LC column containing perfluoroalkyl-modified stationary phase and were separated via gradient elution using a water/methanol/trifluoroacetic acid mixture and trifluoroethanol with formic acid as mobile phases. Matrix-induced signal suppression effects were eliminated because the binary fluorous-labeled amines were strongly retained on the fluorous-phase LC column, whereas the nonfluorous derivatives, including matrix components and monofluorous-labeled compounds such as the derivatization reagent, were poorly retained under the separation conditions. The linear dynamic ranges of the target amines were established over a concentration range of 0.01-1 nM (r > 0.9978), and the limits of detection were found to be 7.8-26 amol on column. The feasibility of this method was further evaluated by applying it to human plasma samples.
authors.affiliation: Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Johnan, Fukuoka 814-0180, Japan.
authors.forename: Tadashi
authors.initials: T
authors.lastname: Hayama
authors.forename: Yohei
authors.initials: Y
authors.lastname: Sakaguchi
authors.forename: Hideyuki
authors.initials: H
authors.lastname: Yoshida
authors.forename: Miki
authors.initials: M
authors.lastname: Itoyama
authors.forename: Kenichiro
authors.initials: K
authors.lastname: Todoroki
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Yamaguchi
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Nohta
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000478:Alkylation; D000588:Amines / Q000097:blood* / Q000138:chemical synthesis; D002853:Chromatography, Liquid / Q000379:methods*; D006801:Humans; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D015394:Molecular Structure; D012680:Sensitivity and Specificity; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D000447:Aldehydes; D000588:Amines; D006845:Hydrocarbons, Fluorinated