biomolecule structure characterization in the gas phase using mass spectrometry生物分子结构表征使用质谱在气相.pdfVIP

Spectroscopy 16 (2002) 71–79 71 IOS Press Biomolecule structure characterization in the gas phase using mass spectrometry Brian Bothner, Laurie Carmitchel, Kristin Staniszewski, Martin Sonderegger and Gary Siuzdak ∗ The Scripps Center for Mass Spectrometry and Department of Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA Abstract. Carbohydrate/cation interactions were examined in the gas phase using mass spectrometry and the results were compared with computer generated models of the complexes. Monosaccharide/alkali cation complexes of five carbohydrates, D-fructose, D-glucose, D-galactose, D-mannose, and a deuterated analog of D-glucose, 6,6-D-glucose-d2 , were studied. Among the technuques used in this effort were electrospray ionization (ESI), desorption/ionization on silicon (DIOS), matrix-assisted laser desorption/ionization (MALDI) and fast atom/ion bombardment (FAB) mass spectrometry. A series of ESI, DIOS, MALDI and FAB-MS experiments were used to obtain relative cation binding preferences of each monosaccharide. Heterodimers of 6,6- D-glucose-d2 formed with each of the monosaccharides show that Na+ binding for D-fructose, D-mannose and D-galactose is similar, while D-glucose was 25% weaker. Modeling studies and energy minimization calculations on the alpha and beta forms of the monosaccharide alkali cation complexes are consistent with the experimental data and indicate that D-fructose, D-galactose, and D-mannose undergo tridentate and tetradentate binding with Na+ and Li+ while D-glucose would only form a bidentate complex. 1. Introduction Alkali cations and carbohydrates are important physiological partners in transport processes. Carbo- hydrate/cation interactions play a role in protein transport across cell membranes [1,2] and cations help maintain appropri