Targeted LC-MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA.
Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add additional fragmentation identifiers, collectively enhancing the abilities for detection and screening of unknown aldehydes. Derivatization can be achieved under mild conditions (pH 5.7, 10 degrees C). By changing the secondary reagent (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide instead of sodium cyanoborohydride), 4-APEBA is also applicable to the selective derivatization of carboxylic acids. Synthesis of the new label, exploration of the derivatization conditions, characterization of the fragmentation of the aldehyde and carboxylic acid derivatives in MS/MS, and preliminary applications of the labeling strategy for the analysis of aldehydes in urine and plasma are described.
Section of Biomolecular Analysis, Faculty of Science, VU University Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Mark
M
Eggink
Maikel
M
Wijtmans
Ansgar
A
Kretschmer
Jeroen
J
Kool
Henk
H
Lingeman
Iwan J P
IJ
de Esch
Wilfried M A
WM
Niessen
Hubertus
H
Irth
D000447:Aldehydes / Q000032:analysis* / Q000378:metabolism; D000814:Aniline Compounds / Q000737:chemistry; D015415:Biomarkers / Q000032:analysis* / Q000378:metabolism; D002264:Carboxylic Acids / Q000032:analysis* / Q000378:metabolism; D002853:Chromatography, Liquid / Q000379:methods*; D004123:Dimethylamines / Q000737:chemistry; D006801:Humans; D015227:Lipid Peroxidation; D013058:Mass Spectrometry / Q000379:methods*; D010084:Oxidation-Reduction; D010949:Plasma / Q000378:metabolism
C547382:4-(2-(trimethylamino)ethoxy)benzeneamine; D000447:Aldehydes; D000814:Aniline Compounds; D015415:Biomarkers; D002264:Carboxylic Acids; D004123:Dimethylamines