三维荧光结合二阶校正法测定蛇床子及人体血浆中蛇床子素的含量

Determination of Osthole in Cnidii Fructus and human plasma using excitation-emission matrix fluorescence with the aid of second-order calibration methods

利用二阶校正的平行因子分析(PARAFAC)算法,交替三线性(ATLD)算法和自加权交替三线性(SWATLD)算法辅助三维荧光对中药蛇床子和人体血浆中蛇床子素进行了定性及定量分析。中药蛇床子和人体血浆体系中背景复杂,与蛇床子素的荧光峰有严重的重叠。然而,PARAFAC算法,ATLD算法和SWATLD算法具有独特的"二阶优势",即使在有未知干扰存在的情况下也能得到令人满意的结果。三种方法测得的蛇床子素在中药蛇床子中的回收率分别为103.6%,101.5%和103.0%,在血浆中的回收率分别为111.1%,100.0%和106.6%,得到的蛇床子素解析光谱和真实光谱几乎完全重合。实验结果说明,这三种化学计量学二阶校正算法可以在有未知干扰组分共存的情况下对蛇床子素进行准确而有效的定性及定量测定。

A novel approach was developed for the direct quantitative and qualitative analysis of osthole in Cnidii Fructus and human plasma by the incorporation of three - dimensional fluorescence with second - order calibration methodologies based on parallel factor analysis （PARAFAC） algorithm, alternating trilinear decomposition （ATLD）, and self- weighted alternating trilinear decomposition （SWATLD） algorithms, respectively. The EEM spectra of the analytes were overlapped with the background in Cnidii Fructus and human plasma samples. However, the second - order advantage of both PARAFAC, ATLD and SWATLD methods was exploited, even in the presence of unknown interferences the satisfactory results can be obtained. The average recoveries of osthole in Cnidii Fruetus by using PARAFAC, ATLD, and SWATLD with an estimated component number of two were 103.6 % , 101.5 % , and 103.0 % , respectively, and in human plasma were 111.1% , 100.0 %, and 106. 6 %, respectively, the resolved osthole spectra and real spectra overlapped almost completely. It demonstrates that the chemometrics “ second order correction” method can be used for the qualitative and quantitative analysis of osthole even in the presence of unknown interferences.