State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
Spectrochim Acta A Mol Biomol Spectrosc. 2017 Mar 15;175:229-238. doi: 10.1016/j.saa.2016.12.030. Epub 2016 Dec 21.
A rapid interference-free spectrofluorometric method combined with the excitation-emission matrix fluorescence and the second-order calibration methods based on the alternating penalty trilinear decomposition (APTLD) and the self-weighted alternating trilinear decomposition (SWATLD) algorithms, was proposed for the simultaneous determination of nephrotoxic aristolochic acid I (AA-I) and aristololactam I (AL-I) in five Chinese herbal medicines. The method was based on a chemical derivatization that converts the non-fluorescent AA-I to high-fluorescent AL-I, achieving a high sensitive and simultaneous quantification of the analytes. The variables of the derivatization reaction that conducted by using zinc powder in acetose methanol aqueous solution, were studied and optimized for best quantification results of AA-I and AL-I. The satisfactory results of AA-I and AL-I for the spiked recovery assay were achieved with average recoveries in the range of 100.4-103.8% and RMSEPs <0.78ngmL, which validate the accuracy and reliability of the proposed method. The contents of AA-I and AL-I in five herbal medicines obtained from the proposed method were also in good accordance with those of the validated LC-MS/MS method. In light of high sensitive fluorescence detection, the limits of detection (LODs) of AA-I and AL-I for the proposed method compare favorably with that of the LC-MS/MS method, with the LODs <0.35 and 0.29ngmL, respectively. The proposed strategy based on the APTLD and SWATLD algorithms by virtue of the "second-order advantage", can be considered as an attractive and green alternative for the quantification of AA-I and AL-I in complex herbal medicine matrices without any prior separations and clear-up processes.
一种快速无干扰的光谱荧光法，结合激发-发射矩阵荧光和基于交替惩罚三线性分解（APTLD）和自加权交替三线性分解（SWATLD）算法的二阶校正方法，被提出用于同时测定五种中草药中的肾毒性马兜铃酸 I（AA-I）和马兜铃内酰胺 I（AL-I）。该方法基于化学衍生化，将非荧光 AA-I 转化为高荧光 AL-I，实现了对分析物的高灵敏度和同时定量。研究并优化了在乙缩醛甲醇水溶液中用锌粉进行衍生化反应的变量，以获得 AA-I 和 AL-I 的最佳定量结果。通过使用标准加入法进行加标回收实验，AA-I 和 AL-I 的结果令人满意，平均回收率在 100.4-103.8%范围内，RMSEPs<0.78ngmL，验证了该方法的准确性和可靠性。从提出的方法中获得的五种草药中的 AA-I 和 AL-I 含量也与经过验证的 LC-MS/MS 方法相符。鉴于高灵敏度荧光检测，该方法对 AA-I 和 AL-I 的检测限（LOD）优于 LC-MS/MS 方法，LOD 分别为<0.35 和 0.29ngmL。基于 APTLD 和 SWATLD 算法的策略，利用“二阶优势”，可以被认为是一种有吸引力的绿色替代方法，用于在没有任何预先分离和净化过程的复杂中草药基质中定量测定 AA-I 和 AL-I。
