Presence Of Uncalibrated Interferences Research Articles

Nonchromatographic analysis of polyphenols in red wine samples: Evaluation of front-face fluorescence spectroscopy and third-order multivariate calibration to quantify catechin and epicatechin

In this work, an analytical approach based on third-order multivariate calibration and front-face fluorescence spectroscopy to determine the levels of (+)-catechin and (-)-epicatechin in wine samples was evaluated. An extra reaction mode (pH gradient) was incorporated into excitation-emission fluorescence second-order data, leading to higher predictivity and selectivity for catechin detection. Application of a Multivariate curve resolution-alternating least squares (MCR-ALS) algorithm resolved the systems, even in the presence of uncalibrated interferences, and yielded suitable figures of merit. Through the method, the level of (+)-catechin was directly determined, and the concentration of (-)-epicatechin was determined by the difference in total catechins (Epi + Cat) between synthetic samples. Finally, the levels of catechin were satisfactorily determined in real wine samples at mg L-1 levels with minimal sample treatment and in accordance with a reference method based on chromatographic separation.

Chromatographic Applications in the Multi-Way Calibration Field.

In this review, recent advances and applications using multi-way calibration protocols based on the processing of multi-dimensional chromatographic data are discussed. We first describe the various modes in which multi-way chromatographic data sets can be generated, including some important characteristics that should be taken into account for the selection of an adequate data processing model. We then discuss the different manners in which the collected instrumental data can be arranged, and the most usually applied models and algorithms for the decomposition of the data arrays. The latter activity leads to the estimation of surrogate variables (scores), useful for analyte quantitation in the presence of uncalibrated interferences, achieving the second-order advantage. Recent experimental reports based on multi-way liquid and gas chromatographic data are then reviewed. Finally, analytical figures of merit that should always accompany quantitative calibration reports are described.

Three efficient chemometrics assisted fluorimetric detection methods for interference-free, rapid, and simultaneous determination of ibrutinib and pralatrexate in various complicated biological fluids

In this study, a series of green, interference-free fluorimetric detection methods of the excitation-emission matrix coupled with the second-order calibration methods were proposed for the determination of ibrutinib and pralatrexate in various complicated biological fluids. The second-order advantage of the proposed method can overcome the problem of poor selectivity caused by the wide spectra of the fluorescence method. Even in the presence of uncalibrated interferences and severe peak overlap, the signal of pure substance and accurate quantitative results were still obtained. The average recoveries of the three methods were 94.5–104.9% for Alternating Trilinear Decomposition (ATLD) algorithm, 95.5–105.8% for Alternating Normalization Weighted Error (ANWE) algorithm and 94.4–105.7% for Parallel Factor Analysis (PARAFAC) algorithm, respectively. For ATLD, ANWE and PARAFAC, the relative standard deviations (RSD) were lower than 9.2%, 6.8% and 9.2%, and the RMSEPs were less than 8.1, 8.4 and 8.6 ng mL−1, respectively. In addition, the elliptic joint confidence region (EJCR) was adopted to further prove the accuracy of the three methods. The results showed that the three methods can accurately be quantified without significant difference. Good figures of merit parameters were also obtained. Among them, the limit of detection (LOD) and limit of quantification (LOQ) of ibrutinib and pralatrexate were in the range of 0.11–0.76 ng mL−1 and 0.21–1.12 ng mL−1, respectively, which were lower than the corresponding blood concentrations. These results indicate that the proposed method provides a promising, alternative and universal analysis strategy for clinical drug monitoring.

On the performance of multivariate curve resolution to resolve highly complex liquid chromatography–full scan mass spectrometry data for quantification of selected immunosuppressants in blood and water samples

Liquid chromatography triple-quadrupole mass spectrometry (LC–MS/MS) in multiple reaction monitoring (MRM) mode is a commonly used approach for quantification of target compounds in complex samples. Regarding the multivariate advantages that can be obtained in the light of full spectra recording, the potential and performance of a smart strategy which is a post-processing of LC–MS full scan data sets with multivariate curve resolution-alternating least squares (MCR-ALS) algorithm for determination of cyclosporine-A (CsA) and tacrolimus (TAC) as typical immunosuppressants in human blood and organic micropollutants in surface water samples was investigated in the current study. Before peak resolution and quantification, LC–MS data compression was performed on each individual and augmented data matrices based on searching the regions of interest (ROIs) in the m/z domain. Then, due to presence of matrix effect, MCR-ALS modeling was performed using a matrix-matched calibration strategy. Here, the serious LC–MS issues such as background drift, chromatographic shifts and co-elution of non-calibrated sample constituents were resolved by implementation of MCR-ALS method on ROI based compressed data. It was shown that the strategy is a powerful tool for the quantitation of CsA and TAC in complex matrices and in the presence of uncalibrated interferences with highly overlapped peaks. However, the overall results indicated that performance of the multivariate modeling of LC–MS in full scan mode for drug quantitation strongly depends on the selected drug, as in the current case superiority of the method for analysis of CsA over TAC, with different therapeutic concentration ranges, was observed.

Simultaneous determination of binary solution of triphenylmethane dyes in complex matrices onto magnetic amino-rich SWCNT using second-order calibration method.

This study suggested a new method for simultaneous quantification of two dyes in complex matrices using second-order data by spectrophotometry. Second-order data was generated simply without any expensive instrument using two independent variables including wavelength and the monotonic addition of sodium dodecyl sulfate. Solid-phase extraction (SPE) based on amino-rich magnetic single-walled carbon nanotube as an adsorbent was employed prior to second-order data generation. SPE optimization was performed by Box-Behnken design, and parameters and their interaction which were dependent on the simultaneous extraction of dyes were examined. Competitive Langmuir and Freundlich isotherms for a binary system and individual dyes could all represent the equilibrium data well. The second-order data was processed by parallel factor analysis (PARAFAC and PARAFAC2) and multivariate curve resolution-alternating least squares (MCR-ALS). Figures of merit of the model including a limit of detection of 3.0 and 2.5ngmL-1 for crystal violet and malachite green, respectively, were estimated using the MCR-ALS method. The combination of the second-order calibration and SPE presents an easy and versatile method for determination of the mixture of two dyes in the presence of uncalibrated interferences in environmental water, synthetic, and fish samples with the recoveries of 94-104.

Multidimensional voltammetry: Four-way multivariate calibration with third-order differential pulse voltammetric data for multi-analyte quantification in the presence of uncalibrated interferences

A four-way multivariate calibration approach based on the combination of differential pulse voltammetric (DPV) data and four-way algorithms is described for the first time. To achieve this goal, the DPV response of each sample was recorded thirty-six times. Six current-potential matrices were recorded at six different pulse durations. Each matrix consists of six vectors which have been recorded at six different pulse heights. The three-way data array obtained for the calibration set and for each of the test samples were joined into a single four-way data array. The recorded four-way data array was nonlinear, thus, the non-linearities were tackled by potential shift correction using correlation-optimized warping (COW) algorithm and subsequently was analyzed with unfolded-partial least squares/residual trilinearization (U-PLS/RTL) and multi-way-PLS/RTL (N-PLS/RTL) as third-order multivariate calibration algorithms. A comprehensive and systematic strategy for comparing the performance of the two algorithms was presented in this work, in particular with a view of practical applications. This comparison was developed to identify which algorithm offers the best predictions for the simultaneous determination of levodopa (LD), carbidopa (CD), methyldopa (MD), acetaminophen (AC), tramadol (TRA), lidocaine (LC), tolperisone (TOP), ofloxacin (OF), levofloxacin (LOF), and norfloxacin (NOF) in the presence of benserazide (BA), dopamine (DP), and ciprofloxacin (COF) as uncalibrated interferences using a multi-walled carbon nanotubes modified glassy carbon electrode (MWCNTs/GCE). This study demonstrated the more superiority of U-PLS/RTL to resolve the complex systems. The results of applying U-PLS/RTL for the simultaneous determination of the studied analytes in human serum samples as experimental cases were also encouraging.

Evaluation of cloud point extraction coupled with fluorescence spectroscopy and multivariate curve resolution–alternating least squares for tributyltin determination in sediment samples

In this work, a new procedure for tributyltin (TBT) detection in marine sediments based on cloud point extraction (CPE) followed by total fluorescence spectroscopy combined with multivariate curve resolution–alternating least squares (MCR–ALS) is proposed. The multivariate model satisfactorily achieved the second order advantage in the presence of uncalibrated interferences, such as butyltin compounds or metallic species that are commonly found in sediment sample extracts. Under optimal conditions, the detection limit reached 3.0μg Sn L−1, and the relative prediction error was lower than 10%. The accuracy of the method was validated with the analysis of a certified sediment sample (marine sediment PACS-2), and there was good agreement between the certified and experimental results. Finally, the proposed methodology was satisfactorily applied to spiked real sediment samples, demonstrating the suitability of the proposed method for TBT detection in contaminated sediment samples.

Chemometric-based determination of polycyclic aromatic hydrocarbons in aqueous samples using ultrasound-assisted emulsification microextraction combined to gas chromatography–mass spectrometry

In the present research, ultrasonic-assisted emulsification-microextraction (USAEME) coupled with gas chromatography–mass spectrometry (GC–MS) has been proposed for analysis of thirteen environmental protection agency (EPA) polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Tetrachloroethylene was selected as extraction solvent. The main parameters of USAEME affecting the efficiency of the method were modeled and optimized using a central composite design (CCD). Under the optimum conditions (9μL for extraction solvent, 1.15% (w/v) NaCl (salt concentration) and 10min for ultrasonication time), preconcentration factor (PF) of the PAHs was in the range of 500–950. In order to have a comprehensive analysis, multivariate curve resolution-alternating least squares (MCR-ALS) as a second-order calibration algorithm was used for resolution, identification and quantification of the target PAHs in the presence of uncalibrated interferences. The regression coefficients and relative errors (REs, %) of calibration curves of the PAHs were in the satisfactory range of 0.9971–0.9999 and 1.17–6.59%, respectively. Furthermore, analytical figures of merit (AFOM) for univariate and second-order calibrations were obtained and compared. As an instance, the limit of detections (LODs) of target PAHs were in the range of 1.87–18.9 and 0.89–6.49ngmL−1 for univariate and second-order calibration, respectively. Finally, the proposed strategy was used for determination of target PAHs in real water samples (tap and hookah waters). The relative recoveries (RR) and the relative standard deviations (RSDs) were 68.4–109.80% and 2.15–6.93%, respectively. It was concluded that combination of multivariate chemometric methods with USAEME-GC–MS can be considered as a new insight for the analysis of target analytes in complex sample matrices.

Chemometrics-assisted excitation–emission fluorescence analytical data for rapid and selective determination of optical brighteners in the presence of uncalibrated interferences

This study describes a novel approach for the simultaneous determination of CBS-X and CXT as widely used optical brighteners in household detergent, by combining the advantage of the high sensitivity of molecular fluorescence, and the selectivity of second-order chemometric methods. The proposed method is assisted by second-order chemometric analyses employing the PARAFAC, SWATLD and APTLD that help us to determine CBS-X and CXT in laundry powders and environmental samples, through the unique decomposition of the three-way data array. Proposed method can provide the extraction of relative concentrations of the analytes, as well as the spectral profiles. This approach achieves the second-order advantage and in principle could be able to overcome the spectral uncalibrated interference problems in the determination of CBS-X and CXT at the ng g−1 level.By spiking the known concentrations of these compounds to the real samples, the accuracy of the proposed methods was validated and recoveries of the spiked values were calculated. High recoveries (90.00%–113.33%) for the spiked laundry powders and real environmental samples indicate the present method successfully faces this complex challenge without the necessity of applying separation and preconcentration steps in environmental contaminations.

Second-order advantage with excitation–emission photoinduced fluorimetry for the determination of the antiepileptic carbamazepine in environmental waters

A photochemically induced fluorescence system combined with second-order chemometric analysis for the determination of the anticonvulsant carbamazepine (CBZ) is presented. CBZ is a widely used drug for the treatment of epilepsy and is included in the group of emerging contaminant present in the aquatic environment. CBZ is not fluorescent in solution but can be converted into a fluorescent compound through a photochemical reaction in a strong acid medium. The determination is carried out by measuring excitation–emission photoinduced fluorescence matrices of the products formed upon ultraviolet light irradiation in a laboratory-constructed reactor constituted by two simple 4W germicidal tubes. Working conditions related to both the reaction medium and the photoreactor geometry are optimized by an experimental design. The developed approach enabled the determination of CBZ at trace levels without the necessity of applying separation steps, and in the presence of uncalibrated interferences which also display photoinduced fluorescence and may be potentially present in the investigated samples. Different second-order algorithms were tested and successful resolution was achieved using multivariate curve resolution-alternating least-squares (MCR-ALS). The study is employed for the discussion of the scopes and yields of each of the applied second-order chemometric tools. The quality of the proposed method is probed through the determination of the studied emerging pollutant in both environmental and drinking water samples. After a pre-concentration step on a C18 membrane using 50.0mL of real water samples, a prediction relative error of 2% and limits of detection and quantification of 0.2 and 0.6ngmL−1 were respectively obtained.

Chemometrics-assisted excitation-emission fluorescence spectroscopy for simultaneous determination of ethoxyquin and tert-butylhydroquinone in biological fluid samples

A novel method applying simple, rapid, effective and inexpensive excitation-emission matrix (EEM) fluorescence spectroscopy coupled with second-order calibration method for simultaneous determination of ethoxyquin (EQ) and tert-butylhydroquinone (TBHQ) contents in biological fluid samples was developed. After a simple data preprocessing that was to insert zeros below the first-order Rayleigh scattering, the second-order calibration method based on the alternating normalization-weighed error (ANWE) algorithm was used to deal with EEM data. Via the introduced “second-order advantage”, the individual concentrations of the analytes of interest could be obtained even in the presence of uncalibrated interferences. The experimental concentration ranges for the analytes were as follows: EQ, from 4.58 to 20.6 μg mL−1 in plasma and from 6.87 to 20.6 μg mL−1 in urine; TBHQ, from 4.49 to 20.2 μg mL−1 in plasma and from 6.73 to 22.4 μg mL−1 in urine. The recoveries from spiked biological fluid samples were in the ranges of 92.8%–106.2% for EQ and 94.6%–107.2% for TBHQ. These results demonstrate that the three-dimensional EEM fluorescence with second-order calibration method is a powerful tool for obtaining both EQ and TBHQ quantitative results in plasma and urine samples, and could be applied to more complex matrices.

Measuring estriol and estrone simultaneously in liquid cosmetic samples using second-order calibration coupled with excitation–emission matrix fluorescence based on region selection

This paper describes a sensitive excitation–emission matrix fluorescence (EEM) method for simultaneously measuring contents of two estrogens, estriol (E3) and estrone (E1), in liquid cosmetic samples with the aid of a second-order calibration method based on a parallel factor analysis (PARAFAC) algorithm. Before processing the obtained three-way data, a better region of the excitation and emission spectra was purposely selected. Then PARAFAC was recommended to acquire the clean spectra and predict the individual concentrations of the analytes of interest even in the presence of uncalibrated interferences. The standard curves of the two analytes are linear within a linear concentration range of 0–0.736 μg mL−1 of E3 and 0–18.000 μg mL−1 of E1 with correlation coefficients typically greater than 0.99. In the analysis of watermelon frost anti-acne toner sold on the internet web site, the limit of detection (LOD) of E3 is 4.7 ng mL−1 with an accuracy of 102.3–113.7%, and for E1, the LOD is 96.1 ng mL−1 with an accuracy of 92.3–111.0%. In the analysis of pagoda flower relaxing lotion from the commercial market in Changsha, the LOD of E3 is 8.9 ng mL−1 with an accuracy of 95.0–107.1%, and for E1, the LOD is 76.9 ng mL−1 with an accuracy of 98.6–119.3%. Generally, a new avenue has been opened up to determine estrogens quantitatively in cosmetic samples. This methodology will achieve greater development and gradually become a more routine approach in cosmetic quality control due to its advantages of high sensitivity, simple pretreatment procedure and non-destructive nature.

Spectrofluorimetry in organized media coupled to second-order multivariate calibration for the determination of galantamine in the presence of uncalibrated interferences

The present article describes the spectrofluorimetric determination of galantamine, a widely used acetylcholinesterase inhibitor, through excitation–emission fluorescence matrices and second-order calibration. With the purpose of enhancing the fluorescence intensity of this substance, the effect of different organized assemblies was evaluated. Although the interaction of galantamine with different cyclodextrins is weak, it was corroborated that the fluorescence intensity of this pharmaceutical in the presence of α-cyclodextrin is increased by a twofold factor. Among the studied micellar media, the anionic surfactant sodium dodecyl sulfate produced the largest signals for the compound of interest (sixfold enhancement), and was selected as auxiliary reagent for the subsequent determinations. The developed approach enabled the determination of galantamine at the ng mL −1 level without the necessity of applying separation steps, and in the presence of uncalibrated interferences. The applied second-order chemometric tools were parallel factor analysis (PARAFAC), unfolded partial least-squares coupled to residual bilinearization (U-PLS/RBL), and multidimensional partial least-squares coupled to residual bilinearization (N-PLS/RBL). The ability of U-PLS/RBL to successfully overcome spectral interference problems is demonstrated. The quality of the proposed method was established with the determination of galantamine in both artificial and natural water samples.

Second-order advantage with excitation-emission fluorescence spectroscopy and a flow-through optosensing device. Simultaneous determination of thiabendazole and fuberidazole in the presence of uncalibrated interferences

This paper presents a novel approach for the simultaneous determination of two widely used fungicides in a very interfering environment, combining the advantage of a spectrofluorimetric optosensor coupled to a flow-injection system and the selectivity of second-order chemometric algorithms. The sensor is based on the simultaneous retention of thiabendazole and fuberidazole on C18-bonded phase placed inside a flow-cell. After the arrival of the analytes to the sensing zone, the flow is stopped and the excitation-emission fluorescence matrix is read in a fast-scanning spectrofluorimeter. Parallel factor analysis (PARAFAC) and unfolded and multidimensional partial least-squares coupled to residual bilinearization (U- and N-PLS/RBL) were selected for data processing. These algorithms achieve the second-order advantage, and are in principle able to overcome the problem of the presence of unexpected interferences. The power of U-PLS/RBL to quantify both fungicides at parts-per-billion levels, even in the presence of high concentrations of spectral interferences such as carbaryl, carbendazim and 1-naphthylacetic acid, is demonstrated. Indeed, U-PLS/RBL allowed us to reach selectivity using a commercial but non-selective sensing support. To the best of our knowledge, this is the first time the potentiality of the 'second-order advantage' is evaluated on a flow-injection system, using an unspecific supporting material and in the presence of three real interferences. Using a sample volume of 2 mL, detection limits of 4 ng mL(-1) and 0.3 ng mL(-1) for thiabendazole and fuberidazol were respectively obtained in samples without interferences. In samples containing interferences, the limits of detection were 17 and 1 ng mL(-1) for thiabendazole and fuberidazol, respectively. The sample frequency, including excitation/emission fluorescence matrix measurements, was 12 samples h(-1). The sensor was satisfactorily applied to the determination of both analytes in real water samples.

Time-alignment of bidimensional chromatograms in the presence of uncalibrated interferences using parallel factor analysis: Application to multi-component determinations using liquid-chromatography with spectrofluorimetric detection

A new methodology for the alignment of matrix chromatographic data is proposed, based on the decomposition of a three-way array composed of a test and a reference data matrix using a suitably initialized and constrained parallel factor (PARAFAC) model. It allows one to perform matrix alignment when the test data matrix contains unexpected chemical interferences, in contrast to most of the available algorithms. A series of simulated analytical systems is studied, as well as an experimental one, all having calibrated analytes and also potential interferences in the test samples, i.e., requiring the second-order advantage for successful analyte quantitation. The results show that the newly proposed method is able to properly align the different data matrix, restoring the trilinearity which is required to process the calibration and test data with second-order multivariate calibration algorithms such as PARAFAC. Recent models including unfolded partial least-squares regression (U-PLS) and N-dimensional PLS (N-PLS), combined with residual bilinearization (RBL), are also applied to both simulated and experimental data. The latter one corresponds to the determination of the polycyclic aromatic hydrocarbons benzo[ b]fluoranthene and benzo[ k]fluoranthene in the presence of benzo[ j]fluoranthene as interference. The analytical figures of merit provided by the second-order calibration models are compared and discussed.

Quantitative Analysis of Epinephrine in Human Plasma Samples Using Kinetic Fluorometric Method Combined with Second-order Calibration

A kinetic fluorometric method was proposed for the quantitative determination of epinephrine (EP) in human plasma samples with the aid of second-order calibration methods based on alternating trilinear decomposition (ATLD) and alternating fitting residue (AFR) algorithms. It was based on that EP could be gradually converted to a highly fluorescent intermediate product by an oxidation reaction, and further to a non-fluorescent degradation product (o-quinone). These methodologies fully exploit the second-order advantage of the employed three-way kinetic fluorescence data, allowing the concentrations of EP to be quantified even in the presence of uncalibrated interferences. The average recoveries obtained from ATLD and AFR with a factor number of 2 (N = 2) were 100.7 +/- 3.3 and 100.4 +/- 2.2%, respectively. In addition, elliptical joint confidence region (EJCR) tests as well as figures of merit (FOM) were employed to evaluate the accuracy of the two algorithms.

Studying the Interaction of Pirarubicin with DNA and Determining Pirarubicin in Human Urine Samples: Combining Excitation -Emission Fluorescence Matrices with Second-order Calibration Methods

In this paper, UV-vis spectroscopy and fluorescence were combined to study the binding of Calf thymus DNA (ct-DNA) with the anthacycline antibiotic drug pirarubicin (THP). Ethidium bromide (EB) as the fluorescence probe was used to study the competitive binding interactions of THP with DNA by excitation-emission fluorescence matrices (EEFMs) coupled with the parallel factor analysis (PARAFAC) and the alternating normalization-weighted error algorithm (ANWE) with the second-order advantage. All the results conformed that THP mainly bound with DNA by intercalation. Meanwhile, the two second-order calibration methods have been successfully applied to quantify THP in urine samples. Figures of merit were applied to compare the performance of the two methods. The results presented in this work showed that both the PARAFAC and ANWE methods were the convincing way to be applied in the complex biological systems even in the presence of uncalibrated interferences.

Nonlinear Four-Way Kinetic-Excitation−Emission Fluorescence Data Processed by a Variant of Parallel Factor Analysis and by a Neural Network Model Achieving the Second-Order Advantage: Malonaldehyde Determination in Olive Oil Samples

Four-way data were obtained by recording the kinetic evolution of excitation-emission fluorescence matrices for the product of the Hantzsch reaction between the analyte malonaldehyde and methylamine. The reaction product, 1,4-disubstituted-1,4-dihydropyridine-3,5-dicarbaldehyde, is a highly fluorescent compound. The nonlinear nature of the kinetic fluorescence data has been demonstrated, and therefore the four-way data were processed with parallel factor analysis combined with a nonlinear pseudounivariate regression, based on a quadratic polynomial fit, and also with a recently introduced neural network methodology, based on the combination of unfolded principal component analysis, residual trilinearization, and radial basis functions. The applied chemometric strategies are not only able to adequately model the nonlinear data but also to successfully determine malonaldehyde in olive oil samples. This is possible since the experimentally recorded four-way data, modeled with the above-mentioned advanced chemometric approaches, permit the achievement of the second-order advantage. This allows us to predict the analyte concentration in a complex background, in spite of the nonlinear behavior and in the presence of uncalibrated interferences. The present work is a new example of the use of higher-order data for the resolution of a complex nonlinear system, successfully employed in the context of food chemical analysis.

Direct determination of reserpine in urine using excitation-emission fluorescence combined with three-way chemometric calibration methodologies

The concentration of reserpine in urine was directly and quantitatively measured by using the excitation-emission fluorescence (EEM) combined with three-way calibration methodologies. Two calibration methods are based on the alternating trilinear decomposition (ATLD) and the self-weighted alternating trilinear decomposition (SWATLD) algorithms, respectively. These chemometric methodologies have the second-order advantage, which is the ability to get accurate concentration estimates of interested analyte(s) even in the presence of uncalibrated interferences. The satisfactory results on spiked urine samples are obtained, when the component number was chosen to 3 (N = 3) for both the methods. This experiment is easily carried out without time-consuming and complicated pretreatment. It has proved that the three-way calibration methodologies based on ATLD and SWATLD can be feasible to directly quantify the medical content of reserpine in urine.

Simultaneous determination of 6-methylcoumarin and 7-methoxycoumarin in cosmetics using three-dimensional excitation–emission matrix fluorescence coupled with second-order calibration methods

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.