Rapid, Direct Analysis of Cholesterol by Charge Labeling in Reactive Desorption Electrospray Ionization

Chunping Wu, Demian R. Ifa, Nicholas E. Manicke and R. Graham Cooks*
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907
Anal. Chem., 2009, 81 (18), pp 7618–7624
DOI: 10.1021/ac901003u
Publication Date (Web): August 19, 2009
Copyright © 2009 American Chemical Society
* Corresponding author e-mail: cooks@purdue.edu.

Abstract

Direct and rapid analysis of cholesterol was accomplished in the ambient environment using reactive desorption electrospray ionization (DESI) mass spectrometry. This was achieved by electrospraying reagent solutions in the form of high velocity charged droplets at surfaces such as dried serum samples and animal tissue sections. Betaine aldehyde, incorporated into the spray solvent, reacts selectively and rapidly with the alcohol group of cholesterol by nucleophilic addition, forming a hemiacetal salt. Limits of detection for pure cholesterol and related compounds were 1 ng when a solution of cholesterol of 1 μg/mL was spotted onto the surface. Quantitative analysis of free cholesterol in serum using reactive DESI was demonstrated using cholesterol-d7 as internal standard. High throughput analysis of small volumes of serum spotted onto a suitable substrate was achieved at an analysis rate of 14 s per sample, with a relative standard deviation (RSD) of ca. 6%. Use of reactive DESI in the imaging mode allowed 2D spatial distributions of phospholipids and cholesterol to be recorded simultaneously in rat brain tissues.

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History

  • Published In Issue September 15, 2009
  • Article ASAPAugust 19, 2009
  • Received: May 8, 2009
    Accepted: July 31, 2009

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