Incremented alkyl derivatives enhance collision induced glycosidic bond cleavage in mass spectrometry of disaccharides.
Electrospray ionization and collision induced dissociation on a triple quadrupole mass spectrometer were used to determine the effect of spatial crowding of incremented alkyl groups of two anomeric pairs of peralkylated (methyl to pentyl) disaccharides (maltose/cellobiose and isomaltose/gentiobiose). Protonated molecules were generated which underwent extensive fragmentation under low energy conditions. For both the 1 --> 4 and 1 --> 6 alpha and beta isomers, at comparable collision energies the methyl derivative exhibited the least fragmentation followed by ethyl, propyl, butyl, and pentyl. Collision energy is converted to rotational-vibrational modes in competition with bond cleavage, as represented by the slope of product/parent ion (D/P) ratio versus offset energy. Variable rotational freedom at the glycosidic linkage with incremented alkyl groups is hypothesized to be responsible for this effect. Discrimination of anomeric configuration was also assessed for these stereoiosmeric disaccharides. A systematic study showed that an increasing discrimination was attained for the 1 --> 4 isomeric pair as the size of the derivative increased from methyl to pentyl. No anomeric discrimination was attained for the 1 --> 6 isomeric pair. Parent and product ion scans confirmed the consistency of fragmentation pathways among derivatives. Chem-X and MM3 molecular modeling programs were used to obtain minimum energy structures and freedom of motion volumes for the permethylated disaccharides. The modeling results correlated with the fragmentation ratios obtained in the mass spectrometer giving strong indication that the collision induced spectra are dependent on the freedom of rotational motion around the glycosidic bond.
Mendonca
Sanford
S
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
Cole
Richard B
RB
Zhu
Junhua
J
Cai
Yang
Y
French
Alfred D
AD
Johnson
Glenn P
GP
Laine
Roger A
RA
D000465:Algorithms; D000478:Alkylation; D002475:Cellobiose / Q000138:chemical synthesis; D004187:Disaccharides / Q000138:chemical synthesis / Q000737:chemistry*; D006027:Glycosides / Q000737:chemistry*; D008968:Molecular Conformation; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
D004187:Disaccharides; D006027:Glycosides; D002475:Cellobiose; C100052:gentiobiose