Boutreau Laurence, Léon Emmanuelle, Salpin Jean-Yves, Amekraz Badia, Moulin Christophe, Tortajada Jeanine
Laboratoire Analyse et Environment, UMR CNRS 8587, Université d'Evry d'Essonne Bât des Sceinces, Cedex, France.
Eur J Mass Spectrom (Chichester). 2003;9(4):377-90. doi: 10.1255/ejms.567.
The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings.
通过质谱实验研究了最常见的未衍生化己糖异构体的分析区别。电喷雾电离和串联质谱用于分析银和铜配位的单糖（D-葡萄糖、D-半乳糖、D-果糖、O-甲基-α-D-葡萄糖和O-甲基-β-D-葡萄糖）。结果表明，Ag(+)阳离子化可区分前三种单糖，而Cu(+)与这三种单糖形成的配合物表现出相似的反应性，这使得立体异构体难以区分。与铜不同，α和β异头物O-甲基-D-葡萄糖的银加合离子表现出特定的分解模式（即α异头物失去甲醇，β异头物失去氢化银），这便于进行表征。基于密度泛函理论（DFT）计算，对两种异头物的选定配合物进行了理论研究，以便合理解释实验结果。
