TY - JOUR
T1 - Development of sensitive derivatization method for aldosterone in liquid chromatography-electrospray ionization tandem mass spectrometry of corticosteroids
AU - Yamashita, Kouwa
AU - Okuyama, Mitsunobu
AU - Nakagawa, Risa
AU - Honma, Seijiro
AU - Satoh, Fumitoshi
AU - Morimoto, Ryo
AU - Ito, Sadayoshi
AU - Takahashi, Madoka
AU - Numazawa, Mitsuteru
N1 - Funding Information:
This work was supported in part by a High Technology Research Center Project from the Ministry of Education, Culture, Sports and Technology of Japan.
PY - 2008/7/25
Y1 - 2008/7/25
N2 - A highly sensitive quantification method of aldosterone by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was investigated in a positive mode using recently developed picolinyl derivatization. Aldosterone was smoothly and quantitatively converted to the ethyl ether-picolinyl derivative by treatment with HCl-ethanol followed by the esterification with picolinic acid in the presence of 2-methyl-6-nitrobenzoic anhydride and 4-dimethylaminopyridine. The positive ion-ESI mass spectrum of the ethyl ether-picolinyl derivative was characterized by an appearance of protonated molecule ([M+H]+) as a base peak. The ethyl ether-picolinyl derivatization gave a successful result in a separation of aldosterone from corticosterone, dehydrocorticosterone and cortexolone, and also provided an approximately 10-fold higher ESI response in the positive-LC-ESI-MS/MS (selected reaction monitoring; SRM) when compared to that of underivatized molecule (negative mode). The limit of quantification of aldosterone by SRM using ethyl ether-picolinyl derivatization (m/z 494 → m/z 448) was 1 pg/0.2 ml serum with accuracy and precision of 92.6% and 5.6%, respectively.
AB - A highly sensitive quantification method of aldosterone by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was investigated in a positive mode using recently developed picolinyl derivatization. Aldosterone was smoothly and quantitatively converted to the ethyl ether-picolinyl derivative by treatment with HCl-ethanol followed by the esterification with picolinic acid in the presence of 2-methyl-6-nitrobenzoic anhydride and 4-dimethylaminopyridine. The positive ion-ESI mass spectrum of the ethyl ether-picolinyl derivative was characterized by an appearance of protonated molecule ([M+H]+) as a base peak. The ethyl ether-picolinyl derivatization gave a successful result in a separation of aldosterone from corticosterone, dehydrocorticosterone and cortexolone, and also provided an approximately 10-fold higher ESI response in the positive-LC-ESI-MS/MS (selected reaction monitoring; SRM) when compared to that of underivatized molecule (negative mode). The limit of quantification of aldosterone by SRM using ethyl ether-picolinyl derivatization (m/z 494 → m/z 448) was 1 pg/0.2 ml serum with accuracy and precision of 92.6% and 5.6%, respectively.
KW - Aldosterone
KW - Derivatization
KW - Electrospray ionization tandem mass spectrometry
KW - High-performance liquid chromatography
KW - Picolinyl ester
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U2 - 10.1016/j.chroma.2008.05.034
DO - 10.1016/j.chroma.2008.05.034
M3 - Article
C2 - 18561939
AN - SCOPUS:46049093356
VL - 1200
SP - 114
EP - 121
JO - Journal of Chromatography A
JF - Journal of Chromatography A
SN - 0021-9673
IS - 2
ER -