Nagy Gabe, Pohl Nicola L B
Department of Chemistry, Indiana University, Bloomington, IN, 47405, USA.
J Am Soc Mass Spectrom. 2015 Apr;26(4):677-85. doi: 10.1007/s13361-014-1072-z. Epub 2015 Feb 5.
The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.
首次提出了一种分析方法，用于鉴定和确定所有24种醛己糖和2-酮己糖异构体的绝对构型，包括阿洛糖、阿卓糖、半乳糖、葡萄糖、古洛糖、艾杜糖、甘露糖、塔罗糖、果糖、阿洛酮糖、山梨糖和塔格糖的D型和L型对映体。发现了两种独特的固定配体动力学方法组合，以产生足够大的能量差异，从而实现对所有24种己糖的手性区分。这24种己糖中的每一种都产生特定一对碎片离子的独特比例，从而能够同时确定鉴定结果和绝对构型。这种基于质谱的方法可轻松用于准确鉴定来自未知生物来源的任何分离单糖。这项工作朝着完全从头进行碳水化合物分析的目标迈出了关键一步。
