Amine-Functionalized ZIF-8 as a Fluorescent Probe for Breath Volatile Organic Compound Biomarker Detection of Lung Cancer Patients

Abstract

The highly thermally and chemically stable imidazole framework ZIF-8 samples were separately postmodified with amine groups by using <i>N</i>,<i>N</i>'-dimethylethylenediamine (MMEN) and <i>N</i>,<i>N</i>-dimethylaminoethylamine (MAEA), which had the same molecular formula but different structures. The modified ZIF-8 samples (ZIF-8@amine) were thoroughly characterized, including powder X-ray diffractometry, Fourier-transformed infrared spectroscopy, and physical adsorption at 77 K by nitrogen, thermogravimetric analysis, and photophysical characterization. Results showed that after modification, the Brunauer-Emmett-Teller surface area and total pore volume both increased, almost one time higher than those of the original ZIF-8 sample, and followed the order: ZIF-8-MMEN > ZIF-8-MAEA > ZIF-8. Furthermore, the N-H group was successfully grafted into the modified ZIF-8 samples. To examine the sensing properties of the modified ZIF-8@amine samples toward the breath biomarkers of lung cancer, five potential volatile organic compound biomarkers were used as analytes. ZIF-8-MMEN and ZIF-8-MAEA revealed a unique capacity for sensing hexanal, ethylbenzene, and 1-propanol with high efficiency and sensitivity. The three samples all did not show sensing ability toward styrene and isoprene. In addition, ZIF-8, ZIF-8-MMEN, and ZIF-8-MAEA all can sense hexanal with a detection limit as low as 1 ppb.