posted on 2004-05-12, 00:00authored byRebecca A. Jockusch, Romano T. Kroemer, Francis O. Talbot, Lavina C. Snoek, Pierre Çarçabal, John P. Simons, Martina Havenith, Joost M. Bakker, Isabelle Compagnon, Gerard Meijer, Gert von Helden
The β(1→4) glycosidic linkage found in lactose is a prevalent structural motif in many
carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside
isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully
resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure
computed ab initio. This has glycosidic torsion angles of φH (H1−C1−O−C4‘) ≈ 180° and ψH (C1−O−C4‘−H4‘) ≈ 0° which correspond to a rotation of ∼150° about the glycosidic bond compared to the accepted
solution-phase conformation. We discuss the biological implications of this discovery and the generality of
the strategies employed in making it.