Gas chromatography-mass spectrometry of some prostanoids with new derivatizing agents. Application to the analysis of 13,14-dihydro-15-ketoprostaglandin F2 alpha.
13,14-Dihydro-15-ketoprostaglandin (PG) F2 alpha was separated completely from PGD2, PGE2 and PGF2 alpha within 10-15 min by gas chromatography-selected-ion monitoring on a capillary column after conversion to their methyl ester-n-butyloxime-dimethylisopropylsilyl (ME-nBO-DMiPS) ether or ME-nBO-cyclic diethylsilylene (DES) derivatives. The mass spectra were characterized by their inherent ions of [M-43]+ at m/z 596 for the ME-nBO-DMiPS ether and of [M-73]+ at m/z 450 for the ME-nBO-DES derivatives, respectively. The appearance of the characteristic ions in the high-mass region with relatively high intensity and the use of these ions in selected-ion monitoring in a high-resolution mode (M/delta M = 3500) made it possible to enhance the selectivity in the detection of 13,14-dihydro-15-keto-PGF2 alpha in biological fluids. The detection limit of the ME-nBO-DES derivative of 13,14-dihydro-15-keto-PGF2 alpha was found to be 2 pg with a signal-to-noise ratio of 4:1 when the ion of [M-73]+ was monitored at m/z 450.30.
Yamashita
K
K
Research Laboratories, Nippon Kayaku Co. Ltd., Tokyo, Japan.
Watanabe
K
K
Ishibashi
M
M
Miyazaki
H
H
Yokota
K
K
Horie
K
K
Yamamoto
S
S
D015237:Dinoprost / Q000031:analogs & derivatives*; D008401:Gas Chromatography-Mass Spectrometry; D006801:Humans; D007202:Indicators and Reagents; D011460:Prostaglandins F / Q000032:analysis* / Q000097:blood
D007202:Indicators and Reagents; D011460:Prostaglandins F; C008228:15-keto-13,14-dihydroprostaglandin F2alpha; D015237:Dinoprost