title: Simultaneous determination of 6-methylcoumarin and 7-methoxycoumarin in cosmetics using three-dimensional excitation-emission matrix fluorescence coupled with second-order calibration methods.
abstract: This paper reports a simple, rapid, and effective method for quantitative analysis of 6-methylcoumarin (6-MC) and 7-methoxycoumarin (7-MOC) in cosmetics using excitation-emission matrix (EEM) fluorescence coupled with second-order calibration. After simple pretreatments, the adopted calibration algorithms exploiting the second-order advantage, i.e., parallel factor analysis (PARAFAC) and self-weighted alternating tri-linear decomposition (SWATLD), could allow the individual concentrations of the analytes of interest to be predicted even in the presence of uncalibrated interferences. In the analysis of facial spray, with the external calibration method, the average recoveries attained from PARAFAC and SWATLD with the factor number of 3 (N=3) were 101.4+/-5.5 and 97.5+/-4.1% for 6-MC, and 103.3+/-1.7 and 101.7+/-1.8% for 7-MOC, respectively. Moreover, in the analysis of oil control nourishing toner, the standard addition method (SAM) was suggested to overcome the partial fluorescence quenching of 6-MC induced by the analyte-background interaction, which also yielded satisfactory prediction results. In addition, the accuracy of the two algorithms was also evaluated through elliptical joint confidence region (EJCR) tests as well as figures of merit (FOM), including sensitivity (SEN), selectivity (SEL) and limit of detection (LOD). It was found that both algorithms could give accurate results, only the performance of SWATLD was slightly better than that of PARAFAC in the cases suffering from matrix effects. The method proposed lights a new avenue to determine quantitatively 6-MC and 7-MOC in cosmetics, and may hold great potential to be extended as a promising alternative for more practical applications in cosmetic quality control, due to its advantages of easy sample pretreatment, non-toxic and non-destructive analysis, and accurate spectral resolution and concentration prediction.
authors.affiliation: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
authors.forename: Jin-Fang
authors.initials: JF
authors.lastname: Nie
authors.forename: Hai-Long
authors.initials: HL
authors.lastname: Wu
authors.forename: Shao-Hua
authors.initials: SH
authors.lastname: Zhu
authors.forename: Qing-Juan
authors.initials: QJ
authors.lastname: Han
authors.forename: Hai-Yan
authors.initials: HY
authors.lastname: Fu
authors.forename: Shu-Fang
authors.initials: SF
authors.lastname: Li
authors.forename: Ru-Qin
authors.initials: RQ
authors.lastname: Yu
mesh_terms: D002138:Calibration; D003358:Cosmetics / Q000032:analysis* / Q000737:chemistry; D003374:Coumarins / Q000032:analysis*; D005453:Fluorescence; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D013050:Spectrometry, Fluorescence / Q000379:methods*; D014468:Umbelliferones / Q000032:analysis*
chemical_list: D003358:Cosmetics; D003374:Coumarins; D014468:Umbelliferones; C000317:4-bromomethyl-7-methoxycoumarin; C018096:6-methylcoumarin