Optimization of an online heart-cutting multidimensional gas chromatography clean-up step for isotopic ratio mass spectrometry and simultaneous quadrupole mass spectrometry measurements of endogenous anabolic steroid in urine
| Autor: | Thomas Piper, Francisco Radler de Aquino Neto, Fábio Azamor de Oliveira, Alessandro Casilli, Henrique Marcelo G. Pereira, Monica Costa Padilha, Mario Thevis |
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| Rok vydání: | 2016 |
| Předmět: |
Chromatography
Gas Analytical chemistry Pharmaceutical Science Mass spectrometry Androsterone 01 natural sciences High-performance liquid chromatography Gas Chromatography-Mass Spectrometry Mass Spectrometry Analytical Chemistry law.invention Matrix (chemical analysis) Anabolic Agents law Etiocholanolone Environmental Chemistry Flame ionization detector Humans Sample preparation Testosterone Isotope-ratio mass spectrometry Spectroscopy Chromatography High Pressure Liquid Doping in Sports Carbon Isotopes Chromatography 010405 organic chemistry Chemistry 010401 analytical chemistry Extraction (chemistry) 0104 chemical sciences Steroids Gas chromatography |
| Zdroj: | Drug testing and analysis. 8(11-12) |
| ISSN: | 1942-7611 |
| Popis: | Measuring carbon isotope ratios (CIRs) of urinary analytes represents a cornerstone of doping control analysis and has been particularly optimized for the detection of the misuse of endogenous steroids. Isotope ratio mass spectrometry (IRMS) of appropriate quality, however, necessitates adequate purities of the investigated steroids, which requires extensive pre-analytical sample clean-up steps due to both the natural presence of the target analytes and the high complexity of the matrix. In order to accelerate the sample preparation and increase the automation of the process, the use of multidimensional gas chromatography (MDGC) prior to IRMS experiments, was investigated. A well-established instrumental configuration based on two independent GC ovens and one heart-cutting device was optimized. The first dimension (1D) separation was obtained by a non-polar column which assured high efficiency and good loading capacity, while the second dimension (2D), based on a mid-polar stationary phase, provided good selectivity. A flame ionization detector monitored the 1D, and the 2D was simultaneously recorded by isotope ratio and quadrupole mass spectrometry. The assembled MDGC set-up was applied for measuring testosterone, 5α- and 5β-androstanediol, androsterone, and etiocholanolone as target compounds and pregnanediol as endogenous reference compound. The urine sample were pretreated by conventional sample preparation steps comprising solid-phase extraction, hydrolysis, and liquid-liquid extraction. The extract obtained was acetylated and different aliquots were injected into the MDGC system. Two high performance liquid chromatography steps, conventionally adopted prior to CIR measurements, were replaced by the MDGC approach. The obtained values were consistent with the conventional ones. Copyright © 2016 John Wiley & Sons, Ltd. |
| Databáze: | OpenAIRE |
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