Fabrication of an SPME fiber based on ZnO@GA nanorods coated onto fused silica as a highly efficient absorbent for the analysis of cancer VOCs in water and urine

Abstract

Analysis of volatile organic compounds (VOCs) secreted in urine, blood, breath, etc. is a new method for monitoring the metabolism and biochemistry of the human body. However, due to the complexity of samples, a pre-concentration step is necessary before the final analysis with gas chromatography-mass spectroscopy (GC-MS). Therefore, miniaturized extraction methods such as solid-phase microextraction (SPME) can be a promising and simple pre-concentration technique. Different strategies have been adopted for the fabrication or modification of SPME fibers. This study presents the preparation and characterization of glass optical fibers coated with ZnO nanorods functionalized with gallic acid (ZnO@GA nanorod) as SPME adsorbent in GC-MS. ZnO@GA nanorods were synthesized separately and then coated onto the fibers. The coated fibers were characterized by using field emission scanning electron microscopy coupled with energy dispersive analysis of X-rays (FESEM/EDAX) and Fourier transform infrared spectroscopy (FTIR) techniques. Possessing a high surface to volume ratio of ZnO nanorods and functional groups of GA, the ZnO@GA nanorod-based SPME fibers exhibited good extraction performance for VOCs comparing with the commercial polydimethylsiloxane (PDMS) coated fibers. Under optimal conditions (NaCl concentration, 30% w/v; extraction time of 25 min; pH, 5–7 and stirring rate of 400 rpm) ZnO@GA nanorods coated fibers achieved low detection limits (0.32–4.8 μg/L), low quantification limits (1.8-16.3 μg/L) and good linearity (5–1000 μg/L) for selected VOCs. The repeatability (n = 3) for a single fiber was within the range of 4.1–7.9% (intra-day) and 5.7–9.6% (inter-day) while the reproducibility (n = 3) of fiber-to-fiber were in the range of 4.7% and 9.9%. This method was successfully used for the determination of six VOCs in water and urine with satisfactory recoveries of 90–112%. ZnO@GA nanorod coated fibers, despite possessing a much thinner coating compared to the commercial fibers, revealed a better overall extraction efficiency towards VOCs. These results indicated that the ZnO@GA provided a promising alternative in sample pretreatment and analysis in GC-MS.