Role of nitrogen lewis basicity in boronate affinity chromatography of nucleosides.
Urinary modified nucleosides have a potential role as cancer biomarkers, and most of the methods used in their study have utilized low-pressure phenylboronate affinity chromatography materials for the purification of the cis-diol-containing nucleosides. In this study, a boronate HPLC column was surprisingly shown not to trap the nucleosides as would be expected from experience with the classic Affigel 601 resin but showed only partial selectivity toward cis-diol groups while other groups exhibited better retention. In aprotic conditions, trapping of nucleosides was possible; however, the selectivity toward cis-diol-containing compounds was lost with the Lewis basicity of available nitrogens being the main determinant of retention. The experimental findings are compared to and confirmed by DFT calculations.
Department of Chemistry, Nucleoside Research and Mass Spectrometry Unit, and Center for Proteomics and Mass Spectrometry, University of Antwerp, Antwerp, Belgium.
Robin
R
Tuytten
Filip
F
Lemière
Eddy L
EL
Esmans
Wouter A
WA
Herrebout
Benjamin J
BJ
van der Veken
Bert U W
BU
Maes
Erwin
E
Witters
Russell P
RP
Newton
Ed
E
Dudley
D001897:Boronic Acids / Q000737:chemistry*; D002846:Chromatography, Affinity / Q000379:methods*; D003198:Computer Simulation; D008345:Manganese / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D009705:Nucleosides / Q000737:chemistry*; D014867:Water / Q000737:chemistry
D001897:Boronic Acids; D009705:Nucleosides; D014867:Water; D008345:Manganese; D009584:Nitrogen