Infrared Photodissociation Spectroscopy of C N , C N and C N.

The gas-phase vibrational spectroscopy of cold C N (n=2-4) anions is investigated in the CC and CN multiple bond stretching region (1700-2250 cm ) by means of infrared photodissociation (IRPD) spectroscopy in a cryogenically cooled ion trap of the corresponding messenger-tagged complexes. The IRPD spectra are assigned to N-terminated linear structures with triplet ground states ( Σ ) based on a comparison with harmonic vibrational frequencies and intensities from density functional theory computations. In contrast to the polyacetylenic C N anions, the linear C-C chains investigated here exhibit cumulenic character, which is most pronounced in C N and decreases with chain length.

'Naked' and hydrated conformers of the conserved core pentasaccharide of N-linked glycoproteins and its building blocks.

N-glycosylation of eukaryotic proteins is widespread and vital to survival. The pentasaccharide unit -Man3GlcNAc2- lies at the protein-junction core of all oligosaccharides attached to asparagine side chains during this process. Although its absolute conservation implies an indispensable role, associated perhaps with its structure, its unbiased conformation and the potential modulating role of solvation are unknown; both have now been explored through a combination of synthesis, laser spectroscopy, and computation.

Carbohydrate-aromatic interactions: vibrational spectroscopy and structural assignment of isolated monosaccharide complexes with p-hydroxy toluene and N-acetyl l-tyrosine methylamide.

The nature of carbohydrate binding first to p-hydroxy toluene and then the capped amino acid, N-acetyl l-tyrosine methyl amide (AcTyrNHMe), has been investigated in a solvent-free environment under molecular beam conditions. A combination of double resonance IR-UV spectroscopy and quantum chemical calculations has established the structures of complexes with the α and β anomers of methyl d-gluco- and d-galacto- and l-fucopyranosides (α/βMeGlc, MeGal, MeFuc). The new results, when combined with dispersion-corrected DFT calculations, reveal gas phase structures which are dominated by hydrogen bonding but also with evidence of CH-π bonded interactions in complexes with α/βMeGal.

Structural variability in transition metal oxide clusters: gas phase vibrational spectroscopy of V3O(6-8)+.

We present gas phase vibrational spectra of the trinuclear vanadium oxide cations V(3)O(6)(+)·He(1-4), V(3)O(7)(+)·Ar(0,1), and V(3)O(8)(+)·Ar(0,2) between 350 and 1200 cm(-1). Cluster structures are assigned based on a comparison of the experimental and simulated IR spectra. The latter are derived from B3LYP/TZVP calculations on energetically low-lying isomers identified in a rigorous search of the respective configurational space, using higher level calculations when necessary.

Hydration of sugars in the gas phase: regioselectivity and conformational choice in N-acetyl glucosamine and glucose.

The influence of an acetamido group in directing the preferred choice of hydration sites in glucosamine and a consequent extension of the working rules governing regioselective hydration and conformational choice, have been revealed through comparisons between the conformations and structures of "free" and multiply hydrated phenyl N-acetyl-beta-D-glucosamine (betapGlcNAc) and phenyl beta-D-glucopyranoside (betapGlc), isolated in the gas phase at low temperatures. The structures have been assigned through infrared ion depletion spectroscopy conducted in a supersonic jet expansion, coupled with computational methods. The acetamido motif provides a hydration focus that overwhelms the directing role of the hydroxymethyl group; in multiply hydrated betapGlcNAc the water molecules are all located around the acetamido motif, on the "axial" faces of the pyranose ring rather than around its edge, despite the equatorial disposition of all the hydrophilic groups in the ring.