摘要
人体呼出气中的挥发性有机化合物(VOCs)可作为评价生理或病理条件的生化指标。然而,呼出气成分复杂,且VOCs含量较低,难以达到分析仪器的直接检测要求。因此,建立一种简便、快捷、高效的富集技术对VOCs的直接检测具有重要意义。该文将石墨氮化碳(g-C_(3)N_(4))与金属有机骨架复合,制备了三维纳米花状的g-C_(3)N_(4)/UiO-66固相微萃取涂层,联用GC-MS技术对肺癌患者呼出气中的5种生物标志物(苯、甲苯、乙苯、邻二甲苯和癸醛)进行富集检测。通过FT-IR、TGA、XRD和SEM对复合材料进行系列表征,纳米花状固相微萃取纤维的最佳萃取时间为10 min,最佳萃取温度为60℃,最佳解吸时间和解吸温度分别为3 min和260℃。结果表明,5种VOCs在各自的浓度范围内具有良好的线性关系,相关系数为0.9919~0.9977,检出限为0.16~4.50μg/L,定量限为0.54~9.18μg/L。纤维6次平行测定的日内和日间精密度分别为3.3%~7.3%和4.0%~6.6%。由于复合材料中纳米花状层间通道以及g-C_(3)N_(4)微孔的存在,该复合材料涂层表现出较高的富集效率和良好的重复性。5种VOCs的加标回收率稳定在84.6%~113.2%范围内。最后,将该方法应用于肺癌患者呼出气分析检测,无论是健康人群还是肺癌患者,呼出气中苯的含量普遍较低,甲苯的含量差异性明显且肺癌患者远高于健康人群。所建立的方法有望为肺癌无创早期诊断提供参考价值。
Volatile organic compounds(VOCs)in human exhaled breath can act as biochemical indicators for the objective determination and evaluation of physiological or pathological conditions.In humans,the pathophysiology associated with malignant tumors causes metabolic changes that alter the types and concentrations of VOCs in exhaled breath.However,as exhaled breath has a complex composition and low VOC content,meeting the direct detection requirements of analytical instruments is difficult.Therefore,the direct detection of VOCs in exhaled breath requires the development of a simple,fast,and efficient enrichment technique.In this study,graphitic carbon nitride(g-C_(3)N_(4))and the metal-organic framework UiO-66 were combined to prepare a three-dimensional nanoflower-like g-C_(3)N_(4)/UiO-66 solid-phase microextraction(SPME)coating.The g-C_(3)N_(4)/UiO-66 composite was characterized using Fourier transform infrared spectroscopy,thermogravimetric analysis,X-ray diffraction,and scanning electron microscopy.UiO-66,which exhibited a regular ortho-octahedral structure with sharp corners,was embedded among g-C_(3)N_(4) nanoflowers,and the surface was encapsulated in g-C_(3)N_(4) to form a hydrophobic barrier.Five biomarkers(benzene,toluene,ethylbenzene,o-xylene,and decanal)in the exhaled breath of patients with lung cancer were enriched using the developed SPME fiber and then detected using gas chromatography-mass spectrometry.The optimum extraction time and temperature of the nanoflower-like SPME fiber were 10 min and 60℃,respectively,whereas the optimum desorption time and temperature were 3 min and 260℃,respectively.The adsorption efficiencies of the g-C_(3)N_(4)/UiO-66 composite coating,a single UiO-66 coating,and a 30μm polydimethylsiloxane commercial coating were compared under optimal conditions.The five VOCs showed good linearity in the investigated concentration ranges,with correlation coefficients of 0.9919-0.9977,limits of detection of 0.16-4.50μg/L,and limits of quantification of 0.54-9.18μg/L.The intra-and inter-day precisions for six parallel determinations with the SPME fiber were 3.3%-7.3%and 4.0%-6.6%,respectively.Owing to the presence of nanoflower-like interlayer channels and g-C_(3)N_(4) micropores in g-C_(3)N_(4)/UiO-66,the composite coating exhibited a high enrichment efficiency and good repeatability.The spiked recoveries of the five VOCs were in the range of 84.6%-113.2%.Finally,the method was applied to analyze exhaled breath for the detection of lung cancer.The benzene contents in the exhaled breath of both healthy individuals and patients with lung cancer were generally low.However,the toluene contents differed significantly,with patients with lung cancer having much higher levels than healthy individuals.The established method is expected to provide a reference for the noninvasive early diagnosis of lung cancer.
作者
郝启隆
王景
于丽青
张海霞
HAO Qilong;WANG Jing;YU Liqing;ZHANG Haixia(College of Chemistry and Materials Science,Hebei University,Baoding 071002,China;College of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China)
出处
《色谱》
CAS
CSCD
北大核心
2024年第12期1189-1195,共7页
Chinese Journal of Chromatography
基金
甘肃省科技重大专项(23ZDNA007)~~。
