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Mostrando 1 - 10 de 22
  • Publicación
    Fluorescence properties of flavonoid compounds. Quantification in paprika samples using spectrofluorimetry coupled to second order chemometric tools
    (Elsevier, 2016-04-01) Durán Merás, Isabel; Galeano Díaz, Teresa; Muñoz de la Peña, Arsenio; Monago Maraña, Olga
    The influence of pH on the fluorescence of flavonoid compounds was investigated and the highest fluorescence emission was obtained in basic medium. Selected conditions to improve this signal were: pH 9.5, 0.14 M Britton Robinson buffer and methanol between 5% and 10%. The excitation–emission fluorescence matrices of a set of 36 samples of Spanish paprika were analyzed by means of parallel factor analysis (PARAFAC). Thus, the profiles of possible fluorescence components (PARAFAC loadings) were obtained. One of these profiles was identified by matching PARAFAC scores with LC analysis on the same samples. Two clusters of samples were obtained when score values were plotted against each other. Spectrofluorimetry coupled to second order multivariate calibration methods, as unfolded-partial least squares with residual bilinearization (U-PLS/RBL) and multidimensional-partial least-squares with residual bilinearization (N-PLS/RBL), was investigated to quantify quercetin and kaempferol in those samples. Good results were obtained for quercetin by this approach.
  • Publicación
    Non-destructive fluorescence spectroscopy combined with second-order calibration as a new strategy for the analysis of the illegal Sudan I dye in paprika powder
    (Elsevier, 2020-05) Eskildsen, Carl Emil; Muñoz de la Peña, Arsenio; Galeano Díaz, Teresa; Wold, Jens Petter; Monago Maraña, Olga
    This paper presents a novel strategy for determination of the illegal dye Sudan I in paprika powder. The method is based on fluorescence spectroscopy combined with second-order calibration, which was employed for the first time for this purpose. The method is non-destructive and requires no sample preparation. It was probed that Sudan I exhibited fluorescence; however, the color of paprika samples affected the signal and it was not possible to quantify this adulterant by means of univariate and first-order calibration. To model the effect of variability of color in samples, a central composite experimental design was performed with varying ASTA (American Spices Trade Association) color values and Sudan I concentrations. Different second-order algorithms were tried for quantification. The best results for calibration and validation were obtained from Unfolded-Partial Least-Squares (U-PLS) and Multi-way Partial Least-Squares (N-PLS). The level of detection ranges were 0.4 – 3 mg/g and 0.5 – 3 mg/g for U-PLS and N-PLS, respectively. This was lower than other methods found in the literature.
  • Publicación
    Combination of Liquid Chromatography with Multivariate CurveResolution-Alternating Least-Squares (MCR-ALS) in the Quantitationof Polycyclic Aromatic Hydrocarbons Present in Paprika Samples
    (American Chemical Society, 2016-10-07) Pérez, Rocío L; Escandar, Graciela M.; Muñoz de la Peña, Arsenio; Galeano Díaz, Teresa; Monago Maraña, Olga
    This work presents a strategy for quantitating polycyclic aromatic hydrocarbons (PAHs) in smoked paprikasamples. For this, a liquid chromatographic method withfluorimetric detection (HPLC-FLD) was optimized. To resolve some interference co-eluting with the target analytes, the second-order multivariate curve resolution-alternating least-squares (MCR-ALS) algorithm has been employed combined with this liquid chromatographic method. Among the eight PAHs quantified(fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene) byHPLC-FLD, only in the case offluorene, pyrene, and benzo[b]fluoranthene was it necessary to apply the second-order algorithmfor their resolution. Limits of detection and quantitation were between 0.015 and 0.45 mg/kg and between 0.15 and 1.5 mg/kg,respectively. Good recovery results (>80%) for paprika were obtained via the complete extraction procedure, consisting of anextraction from the matrix and the cleanup of the extract by means of silica cartridges. Higher concentrations of chrysene,benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene were found in the paprika samples, with respect to the maximalamounts allowed for other spices that are under European Regulation (EU) N°2015/1933
  • Publicación
    Non-destructive Raman spectroscopy as a tool for measuring ASTA color values and Sudan I content in paprika powder
    (Elsevier, 2019-02-15) Eskildsen, Carl Emil; Afseth, Nils Kristian; Galeano Díaz, Teresa; Muñoz de la Peña, Arsenio; Wold, Jens Petter; Monago Maraña, Olga
    The aim of this study was developing a non-destructive method for the determination of color in paprika powder as well as for detecting possible adulteration with Sudan I. Non-destructive Raman spectroscopy was applied directly to paprika powder employing a laser excitation of 785 nm for the first time. The fluorescence background was estimated, by fitting a polynomial to each spectrum, and then subtracted. After preprocessing the spectra, some peaks were clearly identified as characteristic from pigments present in paprika. The preprocessed Raman spectra were correlated with the ASTA color values of paprika by partial least squares regression (PLSR). Twenty-five paprika samples were adulterated with Sudan I at different levels and the PLSR model was also obtained. The coefficients of determination (R2) were 0.945 and 0.982 for ASTA and Sudan I concentration, respectively, and the root mean square errors of prediction (RMSEP) were 8.8 ASTA values and 0.91 mg/g, respectively. Finally, different approaches were applied to discriminate between adulterated and non-adulterated samples. Best results were obtained for partial least squares – discriminant analysis (PLS-DA), allowing a good discrimination when the adulteration with Sudan I was higher than 0.5%.
  • Publicación
    Characterization of Spanish Paprika by Multivariate Analysis of Absorption and Fluorescence Spectra
    (Taylor and Francis Group, 2016-04-21) Bartolomé García, Teresa de Jesús; Galeano Díaz, Teresa; Kostrzewa Rutkowska, Z.; Monago Maraña, Olga
    Spanish paprika was clustered on the basis of the Spanish Protected Designation of Origin “Pimentón de La Vera” by molecular absorbance and fluorescence with principal component analysis and parallel factor analysis. Rapid extraction of carotenoids, capsaicinoids, and tocopherols was optimized; the best conditions included ethanol as the extractant, an extraction time of 10 min in an ultrasonic bath, and a sample size of 0.1 g. The procedure provided good precision with a relative standard deviation of 1.2% for four samples. Molecular absorption spectra were obtained from 250 to 600 nm and fluorescence excitation and emission spectra were collected from 200 to 295 nm and 300 to 400 nm, respectively. Forty-eight “Pimentón de La Vera” paprika samples and 19 samples from other origins were characterized. A principal component analysis model was constructed from the absorption spectra and clustering was obtained based on the origin. Parallel factor analysis was performed on the fluorescence data and better characterization of the origin was obtained.
  • Publicación
    Cost-effective fully 3D-printed on-drop electrochemical sensor based on carbon black/polylactic acid: a comparative study with screen-printed sensors in food analysis
    (Springer, 2024) Monago Maraña, Olga; Aouladtayib-Boulakjar, Nadia; Zapardiel Palenzuela, Antonio; García Domínguez, Amabel; Ayllón Pérez, Jorge; Rodríguez Prieto, Álvaro; Claver Gil, Juan; Camacho López, Ana María; González Crevillén, Agustín
    3D-printing technology allows scientist to fabricate easily electrochemical sensors. Until now, these sensors were designed employing a large amount of material, which increases the cost and decreases manufacturing throughput. In this work, a low-cost 3D-printed on-drop electrochemical sensor (3D-PES) was fully manufactured by fused filament fabrication, minimizing the number of printing layers. Carbon black/polylactic acid filament was employed, and the design and several printing parameters were optimized to yield the maximum electroanalytical performance using the minimal amount of material. Print speed and extrusion width showed a critical influence on the electroanalytical performance of 3D-PES. Under optimized conditions, the fabrication procedure offered excellent reproducibility (RSD 1.3% in working electrode diameter), speed (< 3 min/unit), and costs (< 0.01 $ in material cost). The 3D-PES was successfully applied to the determination of phloridzin in apple juice. The analytical performance of 3D-PES was compared with an equivalent commercial on-drop screen-printed electrode, yielding similar precision and accuracy but lower sensitivity. However, 3D-PES provides interesting features such as recyclability, biodegradability, low-cost, and the possibility of being manufactured near the point of need, some of which meets several demands of Green Chemistry. This cost-effective printing approach is a green and promising alternative for manufacturing disposable and portable electroanalytical devices, opening new possibilities not only in on-site food analysis but also in point-of-care testing.
  • Publicación
    Determination of pungency in spicy food by means of excitation-emission fluorescence coupled with second-order chemometric calibration
    (Elsevier, 2018-04) Guzmán Becerra, María; Muñoz de la Peña, Arsenio; Galeano Díaz, Teresa; Monago Maraña, Olga
    Capsaicinoids are a family of compounds responsible for the pungency of spicy foods. In this work, the combination of fluorescence and chemometrics was investigated as a novel quantification method of capsaicinoids in spicy food samples. The excitation–emission matrices (EEMs) of the two major capsaicinoids (capsaicin and dihydrocapsaicin) were identical. Hence, the results were presented as the total content of capsaicinoids. The EEMs of a group of paprika, cayenne and chilli peppers, and of another group of spicy sauces were registered. The decomposition of the EEMs of each group was performed by parallel factor analysis (PARAFAC), obtaining three principal components in each case. After the decomposition, the component corresponding to capsaicinoids was identified by comparison with the profile of a standard mixture of capsaicin and dihydrocapsaicin. In addition, the score values of this component were correlated with the Scoville heat units (SHU) calculated by means of an HPLC–FLD method. Good correlations were obtained in both groups (0.998 and 0.992), confirming the assignation of the component to capsaicinoids. Subsequently, a calibration set was built to carry out the calibration in the spectrofluorimeter, using PARAFAC and U-PLS/RBL as second-order calibration algorithms. Good results for SHU determination were obtained in both groups with both algorithms and when the fluorimetric method was validated by means of liquid chromatographic analysis the relative error of prediction was less than 11.3%.
  • Publicación
    Acrylamide-fat correlation in californian-style black olives using near-infrared spectroscopy
    (MDPI, 2023-09-06) Montero Fernández, Ismael; Martín Tornero, Elísabet; Martín Vertedor, Daniel; Fernández Fernández, Antonio; Monago Maraña, Olga
    Californian-style is one of the most important black table olive elaborations. During its processing, table olives produce acrylamide, a potential carcinogen compound generated during sterilization. In the present study, total fat and acrylamide content in Californian-style table olives were determined and a regression between them was performed (acrylamide concentration range: below limit of detection—2500 ng g−1 and 8–22% for total fat). Nowadays, there are fast and efficient new techniques, such as Near-Infrared Spectroscopy (NIRS) to measure fat content parameters. In that sense, NIRS was used to perform a fat content quantification model in olives in order to indirectly determine acrylamide content. Calibration models for fat quantification were obtained in defatted olive pastes from a unique variety and for olive pastes from different varieties. In the first case, best results were obtained since only one variety was used (R2 = 0.9694; RMSECV = 1.31%; and REP = 8.4%). However, in the second case, results were still acceptable R2 = 0.678, RMSECV = 2.3%, REP = 17.7% and RMSEV = 2.17%. Regression coefficients showed the most influence variables corresponded with fat. The determination coefficient for the fat and acrylamide correlation was high (r = 0.877), being an efficient approach to find out the contribution of fat degradation to acrylamide synthesis in table olives.
  • Publicación
    Untargeted classification for paprika powder authentication using visible – Near infrared spectroscopy (VIS-NIRS)
    (Elsevier, 2021-03) Eskildsen, Carl Emil; Galeano Díaz, Teresa; Muñoz de la Peña, Arsenio; Wold, Jens Petter; Monago Maraña, Olga
    This paper describes a non-destructive screening method for authentication of paprika belonging to the Spanish Protected Designation of Origin (PDO) “Pimentón de La Vera”. Different multivariate classification models were developed in order to differentiate PDO and non-PDO samples, using visible-near infrared spectra as fingerprint for each paprika sample. Sample treatment was not required. Principal component analysis (PCA) was applied in different spectral ranges: 400–2500, 400–800 and 800–2500 nm. In all spectral ranges, PCA was largely able to differentiate PDO from non-PDO samples. Partial least-squares - discriminant analysis (PLS-DA), PCA-linear discriminant analysis (LDA) and PCA-quadratic discriminant analysis (QDA) were used as classification methods in the different spectral ranges. All methods were able to differentiate PDO from non-PDO samples, with error rates (ER) lower than 0.15. The best models were those obtained with PLS-DA in the NIR range (800–2500 nm), showing ERs lower than 0.07 and error indexes (IERROR) (false positives) lower than 0.05.
  • Publicación
    Monitoring of chlorophylls during the maturation stage of plums by multivariate calibration of RGB data from digital images
    (MDPI, 2022-12-22) Domínguez Manzano, Jaime; Muñoz de la Peña, Arsenio; Durán Merás, Isabel; Monago Maraña, Olga::virtual::3179::600; Monago Maraña, Olga; Monago Maraña, Olga; Monago Maraña, Olga
    The methodology developed in this study was based on digital imaging processing of plums harvested in eight different weeks during their ripening process. Mean RGB data, histograms, and matrices of RGB data were used to characterise the ripening stage of the plums, in both qualitative and quantitative approaches, by using classification and quantification chemometric methods. An exploratory analysis of data was performed using principal component analysis (PCA) and parallel factor analysis (PARAFAC) in RGB histograms and matrices data, respectively, showing differences in the colour features since the fourth week of harvesting. In the case of the quantitative approach, high correlation was achieved between the histogram data, using partial least squares (PLS), and total chlorophyll content. In addition, between three-way matrixes and total chlorophyll content, good correlations were obtained applying unfolded-PLS (U-PLS) and N-way-PLS (N-PLS). The most accurate results were obtained on the green channel. Analytical parameters obtained were good, with determination coefficients (R2) higher than 0.91 for all models in the first and second-order multivariate analysis. In addition, relative errors of prediction (REPs) were lower than 12% in all models for the green channel. Therefore, the proposed method was a satisfactory alternative to destructive physiological and biochemical methods in the determination of total chlorophylls in plum samples. In the routine analysis, first-order multivariate calibration with PLS analysis is a good option due to the simplicity of data processing.