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Updated: Jun 14, 2026

An Efficient Sample Preparation Method to Enhance Carbohydrate Ion Signals in Matrix-assisted Laser Desorption/Ionization Mass Spectrometry
Published on: July 29, 2018
Simple and practical derivatization procedure for enhanced detection of carboxylic acids in liquid
Tatsuya Higashi1, Takuya Ichikawa, Shinsuke Inagaki
1School of Pharmaceutical Sciences and Global COE Program, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan. higashi@u-shizuoka-ken.ac.jp
Abstract:
A simple and practical derivatization procedure for increasing the detection responses of carboxylic acids in liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) has been developed. 2-Hydrazinopyridine (HP) and 2-picolylamine (PA) rapidly reacted with biologically and clinically important carboxylic acids [chenodeoxycholic acid, glycochenodeoxycholic acid, prostaglandin E2, 2-(-carboxyethyl)-6-hydroxy-2,7,8-trimethylchroman (gamma-CEHC),alpha-lipoic acid, homovanillic acid (HVA) and 5-hydroxyindole-3-acetic acid] in the presence of 2,2'-dipyridyl disulfide and triphenylphosphine. The resulting HP- and PA-derivatives were highly responsive in ESI-MS operating in the positive-ion mode and gave characteristic product ions during MS/MS, which enabled the sensitive detection using selected reaction monitoring. Among the two reagents, PA was of more practical use; the detection responses of the PA-derivatives were increased by 9-158-fold over the intact carboxylic acids and the limits of detection were in the low femtomole range (1.5-5.6 fmol on column). The PA-derivatization was successfully applied to a biological sample analysis; the derivatization followed by LC-ESI-MS/MS enabled the detection of trace amounts of bile acids, gamma-CEHC and HVA in human saliva with a simple pretreatment, small sample volume and short analysis time.
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