Abstract
The legally defensible identification of the narcotic, analgesic buprenorphine, in biological specimen requires considerable sensitivity due to its low therapeutic dosages and corresponding target concentrations. Application of liquid chromatography-electrospray ionisation-mass spectrometry, which became the default method for buprenorphine detection, is impeded by the disadvantageous fragmentation of the stable precursor ion producing unspecific product ions of comparatively low abundance. A chemical modification to form the N-methylpyridinium ether derivative of buprenorphine is presented to improve the selectivity and sensitivity of its detection by liquid chromatography-mass spectrometry (LC-MS). The reaction of buprenorphine with 2-fluoro-1-methyl-pyridinium-p-toluene-sulfonate and triethylamine as catalyst was accomplished in acetonitrile at an ambient temperature yielding a chemically stable derivative. Fragmentation of the permanently charged precursor ion (m/z = 559) leads to the formation of diagnostic and abundant fragments (e.g. m/z = 443 and 450) representing all parts of the molecule. The application of the technique to the identification of buprenorphine in hair samples demonstrates a high specificity, availability of sufficient qualifier ions and a significant (approximately 8-fold) improvement of detection limits with respect to comparable experiments based on underivatised buprenorphine.
Originalsprache | Englisch |
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Zeitschrift | Journal of mass spectrometry : JMS |
Jahrgang | 43 |
Ausgabenummer | 7 |
Seiten (von - bis) | 974-979 |
Seitenumfang | 6 |
ISSN | 1076-5174 |
DOIs | |
Publikationsstatus | Veröffentlicht - 01.07.2008 |