RESUMEN
In this work, we reported the preparation of the hollow zeolitic imidazolate framework-7 (ZIF-7) via etching ZIF-7 with tannic acid, and further fabricated the hollow ZIF-7 coated fiber for the solid phase microextraction (SPME) of the five volatile biomarkers (acetone, isopropanol, hexanal, hexanol and decanal) generated from breast cancer cell lines. The hollow structure not only endowed higher extraction performance for the SPME of analytes, but also improved the diffusion rate of the analytes inside the hollow ZIF-7. Under the optimal conditions, the hollow ZIF-7 coated fiber offered high extraction capacity (25-153 mg g-1) and enhancement factors (EFs, 2023-11250) for the five biomarkers, good linearity (R2 > 0.9918) of acetone and isopropanol (2.5-500 µg L-1) and hexanol, hexanal, and decanal (1.0-100 µg L-1), low limits of detection (S/N = 3) of 0.07-0.53 µg L-1 and the limit of quantifications (LOQs, S/N = 10) of 0.23-1.76 µg L-1. The precisions (RSDs, %) for intra-day (n = 6), inter-day (n = 5) and fiber-to-fiber (n = 6) were 2.8-7.5%, 4.3-8.5%, and 4.2-14.6%, respectively. The high EFs of the hollow ZIF-7 coated fiber for the five biomarkers resulted from the integrated effects of the large surface area, the unique porous structure, hydrophobic interaction, gate-opening effect, and enhanced properties after etching including faster mass transport, multiple active components, and more exposed active sites. The fabricated hollow ZIF-7 coated fiber lasted at least 140 cycles of extraction/desorption/aging without obvious decrease of extraction ability and no change of crystal structure. Finally, the hollow ZIF-7 coated fiber combined with GC-FID had been successfully used to detect the five biomarkers in the headspace gas of human breast cancer cell lines (MDA-MB-231) and normal mammary cell lines (CCD-1095Sk) with the recoveries of 84-105%. These results revealed the prospect of hollow MOFs as efficient adsorbents for sample pretreatment.