Ma Wanwan, Chen Huan, Hou Hongwei, Hu Qingyuan, Bai Yu
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Key Laboratory of Tobacco Biological Effects and Biosynthesis, China National Tobacco Quality Supervision and Test Center, Zhengzhou, 450001, China.
Anal Bioanal Chem. 2023 Nov;415(27):6771-6783. doi: 10.1007/s00216-023-04954-7. Epub 2023 Sep 30.
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. TiO@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 TiO and COF proves to be effective for the extraction of the target analytes. Under optimal conditions, the developed TiO@COF-based SPME-UHPLC-MS/MS method revealed good linearity (R ≥ 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 TiO@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 TiO@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.
磷脂酰胆碱（PC）和溶血磷脂酰胆碱（LPC）是两种类型的磷脂（PLs），据报道它们与喉癌（LC）和甲状腺癌（TC）等头颈癌密切相关，这使得对它们的分析至关重要。本研究开发了基于TiO@COF的固相微萃取（SPME）与超高效液相色谱-串联质谱（UHPLC-MS/MS）联用技术，用于从少量血清中快速准确地检测七种潜在的PL生物标志物。TiO和COF的组合被证明对目标分析物的萃取有效。在最佳条件下，所开发的基于TiO@COF的SPME-UHPLC-MS/MS方法显示出良好的线性（R≥0.997），PLs的检测限范围为0.05至0.38 ng/mL，萃取回收率和基质效应分别为83.09 - 112.03%和85.38 - 113.67%。作为一种高通量预处理方法，获得了令人满意的2.7 - 10.1%的探针间重现率。最后，基于TiO@COF的SPME-UHPLC-MS/MS方法被应用于分析早期LC患者（n = 15）、早期TC患者（n = 15）和健康志愿者（n = 15）血清样本中的LPC 14:0、LPC 16:0、LPC 18:0、LPC 18:1、LPC 19:0、PC 16:0/18:1和PC 18:0。结果表明，使用正交偏最小二乘判别分析（OPLS-DA）可以有效地将癌症患者与健康对照区分开来。总之，所建立的基于TiO@COF的SPME-UHPLC-MS/MS方法对于血清样本中七种PLs的快速测定是可靠的，对头颈癌的早期诊断具有前景。
