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The conformation of phenyl-substituted monosaccharides (mannose, galactose, and glucose) and their singly hydrated complexes has been investigated in the gas phase by means of a combination of mass selected, conformer specific ultraviolet and infrared double resonance hole burning spectroscopy experiments, and ab initio quantum chemistry calculations. In each case, the water molecule inserts into the carbohydrate at a position where it can replace a weak intramolecular interaction by two stronger intermolecular hydrogen bonds. The insertion can produce significant changes in the conformational preferences of the carbohydrates, and there is a clear preference for structures where cooperative effects enhance the stability of the monosaccharide conformers to which the water molecule chooses to bind. The conclusions drawn from the study of monosaccharide-water complexes are extended to the disaccharide lactose and discussed in the light of the underlying mechanisms that may be involved in the binding of carbohydrate assemblies to proteins and the involvement, or not, of key structural water molecules.

We report the results of high-resolution spectroscopic studies on isolated, jet-cooled [2]rotaxanes. Employing IR absorption spectroscopy, we show how these noncovalently bound, multicomponent molecular systems that so far have been out of reach from high-resolution techniques, can now be characterized at an unprecedented level. IR absorption spectra of prototypical hydrogen-bond assembled rotaxanes as well as their associated threads and macrocycles are shown to provide a direct view on the effects of interlocking the macrocycle and thread, and to offer a straightforward approach for the study of their structural and dynamical properties.

Infrared/UV hole-burning spectroscopy is performed on individual conformers of the protected dipeptide Z-Aib-Pro-NHMe. The extended IR range probed in this study allows one to elucidate both the H-bonding motif (5-7 microm) as well as the backbone structure (7-10 microm). Comparison with DFT calculations shows that the backbone is locally constrained to an alpha-conformation by Aib and to a gamma-turn by Pro. The gamma-turn motif observed here is intriguing since the condensed phase structure is known to be a beta-turn. This is the first actual observation of such a discrepancy, and it emphasizes the subtle balance between intra- and intermolecular forces, which is responsible for the relative stability of the different secondary structure motifs.

The beta(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 phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees 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.