Analysis of Underivatized Amino Acids and Their d/l-Enantiomers by Sheathless Capillary Electrophoresis/Electrospray Ionization-Mass Spectrometry

Capillary electrophoresis/electrospray ionization-mass spectrometry (CE/ESI-MS) was applied to the analysis of underivatized amino acids and the separation of their d/l-enantiomers. Under full-scan mode, all standard protein amino acids were separated and detected at low-femtomole levels using a 130...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2003-03, Vol.75 (6), p.1508-1513
Main Authors: Schultz, Casey L, Moini, Mehdi
Format: Article
Language:English
Subjects:
Amino acids
Amino Acids - blood
Analytical chemistry
Arginine - analysis
Blood vessels
Canavanine - analysis
Chemistry
Electrophoresis, Capillary - methods
Exact sciences and technology
Humans
Infant, Newborn
Ions
Miscellaneous
Phenylketonurias - diagnosis
Spectrometry, Mass, Electrospray Ionization - methods
Spectrum analysis
Stereoisomerism
Tyrosinemias - diagnosis
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Summary:Capillary electrophoresis/electrospray ionization-mass spectrometry (CE/ESI-MS) was applied to the analysis of underivatized amino acids and the separation of their d/l-enantiomers. Under full-scan mode, all standard protein amino acids were separated and detected at low-femtomole levels using a 130-cm-long, 20-μm-i.d., 150-μm-o.d. underivatized fused-silica capillary with 1 M formic acid as the background electrolyte. The CE/ESI-MS technique was also applied to the separation of l-arginine from l-canavanine (a close analogue of arginine where the terminal methylene linked to the guanidine group of arginine is replaced by an oxygen atom) in a complex mixture containing all standard protein amino acids. The utility of CE/ESI-MS in the analysis of real-world samples was demonstrated by the identification of two metabolic diseases (PKU and tyrosinemia) through blood analysis with minimal sample preparation. In addition, the on-line separation of 11 underivatized l-amino acids from their d-enantiomers was achieved by using a 30 mM solution of (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid as the background electrolyte.
ISSN:0003-2700
1520-6882
DOI:10.1021/ac0263925