Van Berkel G J, Quirke J M, Tigani R A, Dilley A S, Covey T R
Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Tennessee 37831-6365, USA.
Anal Chem. 1998 Apr 15;70(8):1544-54. doi: 10.1021/ac971348o.
In this paper, the use of ferrocene-based "electrochemically ionizable" derivatives to enhance ES-MS analysis of simple alcohols, sterols, and phenols is discussed. These derivatives are designed to take advantage of the electrolysis process inherent to operation of the ES ion source for selective ionization. Derivatization procedures, electrochemical character of the derivatives, and the ES-MS operational parameters necessary to maximize electrochemical ionization and to enhance gas-phase detection are presented with reference to ferrocenecarbamate ester derivatives of a variety of alcohol standards, as well as the ferroceneboronate derivative of the diol, pinacol. Tandem mass spectrometric analysis of the derivatives (precursor and product ion spectra) is shown to provide derivative confirmation, enhanced detection, and additional analyte structure information. The utility of this derivatization approach for the selective detection of alcohols in complicated mixtures is demonstrated using a saw palmetto (Serenoa repens) fruit extract known to contain a variety of alcohols at low levels.
本文讨论了使用基于二茂铁的“电化学可电离”衍生物来增强简单醇类、甾醇和酚类的电喷雾质谱（ES-MS）分析。这些衍生物旨在利用电喷雾离子源操作中固有的电解过程进行选择性电离。针对多种醇标准品的二茂铁氨基甲酸酯衍生物以及二醇频哪醇的二茂铁硼酸酯衍生物，介绍了衍生化程序、衍生物的电化学特性以及实现电化学电离最大化和增强气相检测所需的ES-MS操作参数。衍生物的串联质谱分析（前体和产物离子谱）显示可提供衍生物确认、增强检测以及额外的分析物结构信息。使用已知含有低水平多种醇类的锯叶棕（Serenoa repens）果实提取物，证明了这种衍生化方法用于复杂混合物中醇类选择性检测的实用性。
