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.
Tuytten
Robin
R
Department of Chemistry, Nucleoside Research and Mass Spectrometry Unit, and Center for Proteomics and Mass Spectrometry, University of Antwerp, Antwerp, Belgium.
Lemière
Filip
F
Esmans
Eddy L
EL
Herrebout
Wouter A
WA
van der Veken
Benjamin J
BJ
Maes
Bert U W
BU
Witters
Erwin
E
Newton
Russell P
RP
Dudley
Ed
E
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