Building up key segments of N-glycans in the gas phase: intrinsic structural preferences of the alpha(1,3) and alpha(1,6) dimannosides.
The intrinsic conformer specific vibrational spectra of two important subunits of the core pentasaccharide of N-linked glycans, the alpha(1,3) and alpha(1,6) dimannosides, have been recorded in the gas phase. Coupling these measurements with a computational exploration of their conformational landscapes has enabled their conformational assignment and has identified characteristic vibrational signatures associated with particular conformational families-including those that do or do not display inter-ring hydrogen bonding across the glycosidic linkage. In addition, the IR spectra of the monosaccharide moieties provide benchmarks, through which the conformational assignments can be refined. This introduces a general concept of modularity and secondary structure in oligosaccharides--essential for the success of similar studies on larger oligosaccharides in the future.
Carçabal
Pierre
P
Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
Hünig
Isabel
I
Gamblin
David P
DP
Liu
Bo
B
Jockusch
Rebecca A
RA
Kroemer
Romano T
RT
Snoek
Lavina C
LC
Fairbanks
Anthony J
AJ
Davis
Benjamin G
BG
Simons
John P
JP
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D005740:Gases; D008362:Mannosides / Q000737:chemistry*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D011134:Polysaccharides / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
D005740:Gases; D008362:Mannosides; D011134:Polysaccharides