Hydrogen bonds (Hbonds) are important stabilizing forces in biomolecules. However, for glycans in aqueous solution, direct NMR detection of Hbonds is elusive because of their transient nature. Here, we present Isotope based Natural-abundance TOtal correlation eXchange SpectroscopY (INTOXSY), a new H-1-C-13 heteronuclear single quantum coherence-total correlation spectroscopy based method, to extract OH groups' exchange rate constants (k(ex)) for molecules in natural C-13 abundance and show that OH Hbonds can be inferred from "slower" H/D k(ex). We evaluate k(ex), measured with INTOXSY in light of those extracted with line shape analysis. Subsequently, we use a set of common glycans to establish a k(ex), reference basis set and to infer the existence of transient Hbonds involving OH donor groups. Then, we report k(ex) values for a series of mono- and disaccharides, as well as for oligosaccharides sialyl Lewis X and beta-cyclodextrin, and compare the results with those from the reference set to extract Hbond information. Finally, we utilize NMR experimental data in conjunction with molecular dynamics simulations to establish donor and acceptor Hbond pairs. Our exchange rate measurements indicate that OH/OD exchange rates, k(HD), values <10 s(-1) are consistent with transient Hbond OH groups and potential acceptor groups can be uncovered through MD simulations.