Reactive Charged Droplets for Reduction of Matrix Effects in Electrospray Ionization Mass Spectrometry

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• 作者：Dmytro S. Kulyk ; Colbert F. Miller ; Abraham K. Badu-Tawiah
• 刊名：Analytical Chemistry
• 出版年：2015
• 出版时间：November 3, 2015
• 年：2015
• 卷：87
• 期：21
• 页码：10988-10994
• 全文大小：435K
• ISSN：1520-6882

文摘

A new quantitative contained-electrospray (ES) process is described here that employs a movable ES emitter to control the reactivity of charged microdroplets by varying their exposure time with acid vapor. The method allows elimination of ion suppression effects caused by the presence of various surface active compounds that coelute with the analyte. For mixtures, contained-ESI mass spectrometric analysis produces relative ion intensities that reflect the true concentrations of analytes in solution. The mechanism for this effect has been elucidated and ascribed to the generation of fine initial droplets in the presence of a high abundance of protons; together, these two factors eliminate competition for charge and space during ion formation. Examples of analytes tested include steroids, phospholipids, phosphopeptides, and sialylated glycans. At least 1 order of magnitude improvement in detection limits, sensitivity, and accuracy of detection was observed when compared to conventional electrospray.