三维荧光二阶校正法用于尿液样中氢化可的松的定量测定  

Quantitative Analysis of Hydrocortisone in Urine Sample Using Three-dimensional Fluorescence Spectrum Analysis Coupled with Second-order Calibration

作　　者：曹莹[1] 吴海龙[1] 朱绍华[1] 李淑芳[1] 边英超[1] 刘佳[1] 俞汝勤[1] 

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

出　　处：《分析科学学报》2008年第6期621-626,共6页Journal of Analytical Science

基　　金：国家自然科学基金(No.20775025;20435010);国家973预研课题(No.2007CB216404)

摘　　要：本文提出了三维荧光光谱结合二阶校正算法实现人体尿液样中氢化可的松定量测定的新方法。氢化可的松本身的荧光较弱，但与浓硫酸反应后可以生成强荧光的化合物。利用这一特性，采用浓硫酸为氧化剂，设定在激发波长为300-370nm、发射波长为400-580nm范围内测定尿液样中氢化可的松的三维荧光光谱，构建三维响应数据阵，然后运用基于三线性分解的二阶校正算法进行解析。当组分数N取3时，采用基于平行因子分析（PARAFAC）算法的Z-阶校正法的平均回收率为98.6±4.1％，预测残差平方根（RMSEP）为0.0114；采用基于满秩平行因子分析（FRA-PARAFAc）算法的二阶校正法的平均回收率和RMSEP分别为99.3±2.4％和0.0066。两种算法可以得到相近且满意的结果。A novel method for quantitative analysis of hydrocortisone in urine by combining three- dimensional fluorescence spectra with second-order calibration methods based on the alternating least-squares principle was proposed. Hydrocortisone, a weak fluorescent substance, can be transformed into a highly fluorescent product by oxidation in concentrated sulfuric acid where the concentrated sulfuric acid is used as an oxidant. Fluorescence spectra were measured at consecutive time points in excitation range of 300-370 nm and emission range of 400-580nm for each sample. Hence, a given three-way response data array was then analyzed by trilinear decomposition method. Second-order calibration methods based on parallel factor analysis （PARAFAC） and full rank parallel factor analysis （FRA- PARAFAC） algorithms were employed for the quantification of hydrocortisone in urine. The results for both PARAFAC and FRA PARAFAC were very similar with average recovery （AR） and root-mean-squared error of prediction （RMSEP）. When the component number was chosen to 3, the obtained average recoveries were 98.6±4.1% for PARAFAC and 99.3±2.4% for FRA-PARAFAC, respectively. The root-mean-squared errors of prediction were 0.0114 for PARAFAC and 0.0066 for FRA-PARAFAC, respectively.

关 键 词：氢化可的松 三维荧光光谱 三线性分解 二阶校正 平行因子分析算法 满秩平行因子分析算法 

分 类 号：O657.39[理学—分析化学]