Determination of patulin in fruit juice and dried fruit samples by in-tube solid-phase microextraction coupled with liquid chromatography–mass spectrometry

• Published in: Journal of Chromatography A 2009-05, Vol.1216 (18), p.3746-3750
• Main Authors: Kataoka, H., Itano, M., Ishizaki, A., Saito, K.
• Format: Article
• Language: English
• Subjects: Apple juice; apples; Automated sample preparation; automation; Biological and medical sciences; dried fruit; food contamination; Food industries; Fruit and vegetable industries; Fundamental and applied biological sciences. Psychology; In-tube solid-phase microextraction; liquid chromatography; Liquid chromatography–mass spectrometry; Malus; mass spectrometry; microextraction; Mycotoxin; Non alcoholic beverage industries and mineral waters; Patulin; solid phase extraction
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2009.03.017

A simple and sensitive method for the determination of patulin in fruit juice and dried fruit samples was developed using a fully automated method consisting of in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–mass spectrometry (LC–MS). Patulin was separated within 5 min by high-performance liquid chromatography using a Synergi MAX-RP 80A column and water/acetonitrile (80/20, v/v) as the mobile phase. Electrospray ionization conditions in the negative ion mode were optimized for MS detection of patulin. The pseudo-molecular ion [M−H] − was used to detect patulin in selected ion monitoring (SIM) mode. The optimum in-tube SPME conditions were 25 draw/eject cycles of 40 μL of sample using a Carboxen 1006 PLOT capillary column as an extraction device. The extracted patulin was readily desorbed from the capillary by passage of the mobile phase, and no carry-over was observed. Using the in-tube SPME LC–MS with SIM method, good linearity of the calibration curve ( r = 0.9996) was obtained in the concentration range of 0.5–20 ng/mL using 13C 3-patulin as an internal standard, and the detection limit (S/N = 3) of patulin was 23.5 pg/mL. The in-tube SPME method showed >83-fold higher sensitivity than the direct injection method (10 μL injection volume). The within-day and between-day precision (relative standard deviations) were below 0.8% and 5.0% ( n = 6), respectively. This method was applied successfully for the analysis of fruit juice and dried fruit samples without interference peaks. The recoveries of patulin spiked into apple juice were >92%, and the relative standard deviations were