title: Interference-free spectrofluorometric quantification of aristolochic acid I and aristololactam I in five Chinese herbal medicines using chemical derivatization enhancement and second-order calibration methods.
abstract: 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-1, 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-1, 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.
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Yong
authors.initials: Y
authors.lastname: Hu
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China. Electronic address: hlwu@hnu.edu.cn.
authors.forename: Hai-Long
authors.initials: HL
authors.lastname: Wu
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Xiao-Li
authors.initials: XL
authors.lastname: Yin
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Hui-Wen
authors.initials: HW
authors.lastname: Gu
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Rong
authors.initials: R
authors.lastname: Xiao
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Li
authors.initials: L
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Huan
authors.initials: H
authors.lastname: Fang
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.
authors.forename: Ru-Qin
authors.initials: RQ
authors.lastname: Yu
mesh_terms: D000465:Algorithms; D034341:Aristolochic Acids / Q000032:analysis* / Q000737:chemistry; D002138:Calibration; D002853:Chromatography, Liquid; D004365:Drugs, Chinese Herbal / Q000737:chemistry*; D015203:Reproducibility of Results; D013050:Spectrometry, Fluorescence / Q000379:methods*; D053719:Tandem Mass Spectrometry
chemical_list: D034341:Aristolochic Acids; D004365:Drugs, Chinese Herbal; C540320:aristololactam-I; C000228:aristolochic acid I
keywords: Aristolochic acid; Aristololactam; Chinese herbal medicine; Excitation-emission matrix fluorescence; Second-order advantage; Second-order calibration