Premium
Malondialdehyde tagging improves the analysis of arginine oligomers and arginine‐containing dendrimers by HPLC‐MS
Author(s) -
Onofrejova Lucia,
Leitner Alexander,
Lindner Wolfgang
Publication year - 2008
Publication title -
journal of separation science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.72
H-Index - 102
eISSN - 1615-9314
pISSN - 1615-9306
DOI - 10.1002/jssc.200700485
Subject(s) - chemistry , arginine , malondialdehyde , chromatography , peptide , formic acid , high performance liquid chromatography , dendrimer , mass spectrometry , amino acid , biochemistry , combinatorial chemistry , antioxidant
Abstract The selective modification of arginine residues by malondialdehyde (MDA) was used to improve the mass spectrometric analysis of arginine oligomers (Arg x , x = 4, 6, 7, 8, 9) and an arginine‐containing dendrimeric peptide. MDA tagging significantly increased the hydrophobicity of the arginine side‐chain and resulted in improved retention in RP HPLC of the oligoarginines using formic acid as mobile phase additive. This avoided the use of TFA to generate sufficient retention, as TFA was shown to lead to a dramatically reduced sensitivity (up to ten‐fold for Arg 8 and Arg 9 ) as a result of the strong signal suppression by ion pairing with multiple basic residues. MDA modification of Arg oligomers not only resulted in improved detection sensitivity for most of the peptides studied ( e. g ., more than six‐fold for Arg 7 ), but also greatly enhanced the quality of MS/MS spectra, in line with previous results for other peptides. Furthermore, MDA modification helped to identify major side products in a sample of a dendrimeric peptide, a class of peptides that is typically difficult to analyze by MS.