TiO2@COF-based solid-phase microextraction combined with UHPLC-MS/MS for the rapid determination of potential biomarkers of phosphatidylcholines and lysophosphatidylcholines in head and neck cancers

Phosphatidylcholine (PC) and lysophosphatidylcholine (LPC), two types of phospholipids (PLs), have been reported to be closely correlated with head and neck cancers of laryngeal cancer (LC) and thyroid cancer (TC), which make their analysis crucial. TiO2@COF-based solid-phase microextraction (SPME) coupled to UHPLC-MS/MS was developed for the rapid and accurate detection of seven potential PL biomarkers from small amounts of serum in this work. The combination of TiO2 and COF proves to be effective for the extraction of the target analytes. Under optimal conditions, the developed TiO2@COF-based SPME-UHPLC-MS/MS method revealed good linearity (R-2 >= 0.997) with LODs ranging from 0.05 to 0.38 ng/mL for PLs, the extraction recoveries and matrix effects ranging from 83.09-112.03% and 85.38-113.67%, respectively. As a high-throughput pretreatment method, satisfactory probe-to-probe reproducibility rates of 2.7-10.1% were obtained. Finally, the TiO2@COF-based SPME-UHPLC-MS/MS method was applied to analyze LPC 14:0, LPC 16:0, LPC 18:0, LPC 18:1, LPC 19:0, PC 16:0/18:1, and PC 18:0 in serum samples from early LC patients (n = 15), early TC patients (n = 15), and healthy volunteers (n = 15). The results indicated that cancer patients could be effectively differentiated from healthy controls using orthogonal partial least squares discriminant analysis (OPLS-DA). In conclusion, the established TiO2@COF-based SPME-UHPLC-MS/MS method is reliable for the rapid determination of the seven PLs in serum samples, which is promising for early diagnosis of head and neck cancers.