荧光法测定人血液和尿液中的美托拉宗和缬沙坦:从零阶校正到二阶校正的比较  

Fluorescence Method for Determination of Metolazone and Valsartan in Human Serum and Urine:A Comparison from Zero-order to Second-order Calibration Method

作　　者：丁紫微 吴海龙[1] 王小芝 王童 刘浩然 DING Zi-Wei;WU Hai-Long;WANG Xiao-Zhi;WANG Tong;LIU Hao-Ran(State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China)

机构地区：[1]湖南大学化学化工学院,化学生物传感与计量学国家重点实验室,长沙410082

出　　处：《分析化学》2025年第2期224-234,共11页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.22174036,22204049,21775039)资助。

摘　　要：提出了一种二阶校正辅助的三维荧光方法,对人血清和尿液中的两种抗高血压药物美托拉宗(MET)和缬沙坦(VAL)同时进行定性和定量分析,并与零阶和一阶校正方法所获得的定量结果进行比较。结果表明,基于零阶和一阶校正方法不适用于光谱严重重叠和未知干扰共存条件下目标物的精准定量分析。然而,基于交替归一加权残差(ANWE)算法的二阶校正方法具有强大的“数学分离”功能,即使在目标分析物和未知干扰物荧光光谱严重重叠的情况下,仍然能够获得令人满意的结果,利用其分析MET和VAL的相关系数均大于0.99,MET和VAL在血清中的平均回收率分别为104.9%±5.7%和107.8%±9.2%,在尿液中的平均回收率分别为103.7%±8.9%和94.7%±3.8%。考察了本方法的灵敏度(SEN)、选择性(SEL)、检出限(LOD)、定量限(LOQ)、重复性和再现性,结果表明,本方法能够实现人体液中MET和VAL的同时准确定量分析,并有望应用于两种药物的临床分析。A second-order calibration method combined with excitation-emission matrix(EEM)fluorescence spectroscopy was presented for simultaneous quantitative analysis of two anti-hypertensive drugs,metolazone(MET)and valsartan(VAL),in human serum and urine,and the quantitative results were compared with the results obtained by zero-and first-order calibration methods.The results indicated that the methods based on zero-and first-order calibration were inadequate for accurately quantifying the components of interest in cases where severe spectral overlap and unknown interferences coexisted.However,it was possible to obtain satisfactory results with the second-order calibration method based on alternating normalization-weighted error(ANWE)algorithm because of its strong“mathematical separation”,even when the fluorescence spectra of the target analytes and unknown interferents considerably overlapped.Correlation coefficients for both analytes were greater than 0.99,with mean recoveries of 104.9%±5.7%and 107.8%±9.2%for MET and VAL in human serum,and 103.7%±8.9%and 94.7%±3.8%in human urine,respectively.In addition,the sensitivity,selectivity,limit of detection,limit of quantification,repeatability,and reproducibility of the proposed second-order calibration method were thoroughly examined.All results indicated that the established method was capable of achieving simultaneous and accurate quantification of MET and VAL in human body fluids,which was expected to be applied to analysis of both drugs in clinical settings.

关 键 词：化学计量学 交替归一加权残差算法 三维荧光光谱 美托拉宗 缬沙坦 

分 类 号：O657.3[理学—分析化学] R969[理学—化学]