Monolithic silica spin column extraction and simultaneous derivatization of amphetamines and 3,4-methylenedioxyamphetamines in human urine for gas chromatographic-mass spectrometric detection

• Published in: Analytica chimica acta 2010-02, Vol.661 (1), p.42-46
• Main Authors: Nakamoto, Akihiro, Nishida, Manami, Saito, Takeshi, Kishiyama, Izumi, Miyazaki, Shota, Murakami, Katsunori, Nagao, Masataka, Namura, Akira
• Format: Article
• Language: English
• Subjects: 3,4-Methylenedioxyamphetamine - urine; 3,4-Methylenedioxyamphetamines; Amphetamines; Amphetamines - urine; Analytic Sample Preparation Methods - methods; Analytical chemistry; Chemistry; Chromatographic methods and physical methods associated with chromatography; Derivatization; Exact sciences and technology; Gas chromatographic methods; Gas Chromatography-Mass Spectrometry - methods; Gas chromatograph–mass spectrometer; Humans; Limit of Detection; Molecular Structure; Monolithic spin column; Propyl chloroformate; Silicon Dioxide - chemistry; Spectrometric and optical methods
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2009.12.013

A simple, sensitive, and specific method with gas chromatography–mass spectrometry was developed for simultaneous extraction and derivatization of amphetamines (APs) and 3,4-methylenedioxyamphetamines (MDAs) in human urine by using a monolithic silica spin column. All the procedures, such as sample loading, washing, and elution were performed by centrifugation. APs and MDAs in urine were adsorbed on the monolithic silica and derivatized with propyl chloroformate in the column. Methamphetamine- d 5 was used as an internal standard. The linear ranges were 0.01–5.0 μg mL −1 for methamphetamine (MA) and 3,4-methylenedioxymethamphetamine (MDMA) and 0.02–5.0 μg mL −1 for amphetamine (AP) and 3,4-methylenedioxyamphetamine (MDA) (coefficient of correlation ≧0.995). The recovery of APs and MDAs in urine was 84–94%, and the relative standard deviation of the intra- and interday reproducibility for urine samples containing 0.1, 1.0, and 4.0 μg mL −1 of APs and MDAs ranged from 1.4% to 13.6%. The lowest detection limit (signal-to-noise ratio ≧ 3) in urine was 5 ng mL −1 for MA and MDMA and 10 ng mL −1 for AP and MDA. The proposed method can be used to perform simultaneous extraction and derivatization on spin columns that have been loaded with a small quantity of solvent by using centrifugation.