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Cationic Xylene Tag for Increasing Sensitivity in Mass Spectrometry
Poguang Wang1, Qi Zhang1, Yuanyuan Yao1
1Northeastern University, Boston, MA, 02115, USA.
A new reagent, CAX-B (cationic xylyl-bromide), enhances mass spectrometry sensitivity by labeling active hydrogen compounds. This derivatization allows for highly sensitive detection of analytes, even at the attomole level.
Area of Science:
- Analytical Chemistry
- Mass Spectrometry
- Organic Chemistry
Background:
- Derivatization reagents are crucial for enhancing analyte detectability in mass spectrometry.
- Existing methods may lack sensitivity for trace-level analysis.
- Novel reagents are needed to improve sensitivity and simplify analysis.
Purpose of the Study:
- To introduce and evaluate N-(2-(Bromomethyl)benzyl)-N,N-diethylethanaminium bromide (CAX-B) as a derivatization reagent.
- To demonstrate the enhanced sensitivity of CAX-tagged analytes in tandem mass spectrometry.
- To explore the derivatization mechanism and potential applications of CAX-B.
Main Methods:
- Synthesis and characterization of CAX-B.
- Derivatization of active hydrogen-containing compounds with CAX-B.
- Analysis of derivatized analytes using liquid chromatography-matrix-assisted laser desorption/ionization-time-of-flight/time-of-flight mass spectrometry (LC-MALDI-TOF/TOF-MS).
- Investigation of fragmentation pathways and neutral loss mechanisms.
Main Results:
- CAX-B effectively labels compounds with active hydrogens.
- CAX-tagged analytes exhibit high sensitivity in tandem mass spectrometry due to facile formation of characteristic product ions.
- Attomole levels of thymidine, estradiol, and nucleobases were detected using CAX-tagging.
- Selective labeling was observed for analytes with multiple active hydrogens, such as bisphenol A.
Conclusions:
- CAX-B is a potent derivatization reagent for significantly enhancing mass spectrometry sensitivity.
- The reagent's mechanism, involving resonance stabilization and anchimeric assistance, facilitates sensitive detection.
- CAX-B and its analogs hold promise for sensitive analysis of various compounds at trace levels.
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