Persona: Monago Maraña, Olga
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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, OlgaThe 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 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, OlgaThis 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 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, OlgaThis 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 Evaluation of hydrophilic and lipophilic antioxidant capacity in Spanish tomato paste: usefulness of front-face total fluroescence signal combined with PARAFAC(Springer, 2021-12-01) Pardo Botello, Rosario; Chamizo Calero, Fátima; Rodríguez Corchado, Raquel; Torre Carreras, Rosa de la; Galeano Díaz, Teresa; Monago Maraña, OlgaThe hydrophilic and lipophilic antioxidant activities due to the main bioactive components present in Spanish tomato paste samples were studied, using standardized and fluorescent methods. After extraction, phenolic antioxidants (Folin-Ciocalteu method) and total antioxidant activity (TEAC assay) were evaluated, examining differences between hydrophilic and lipophilic extracts corresponding to different samples. Total fluorescence spectra of extracts (excitation-emission matrices, EEMs) were recorded in the front-face mode at two different ranges: 210-300 nm/ 310-390 nm, and 295-350 nm/380-480 nm, for excitation and emission, respectively, in the hydrophilic extracts. In the lipophilic extracts, the first range was 230-283 nm/290-340 nm, while the second range was 315-383 nm/390-500 nm for excitation and emission, respectively. EEMs from a set of 22 samples were analyzed by the second-order multivariate technique Parallel Factor Analysis (PARAFAC). Tentative assignation of the different components to the various fluorophores of tomato was tried, based on literature. Correlation between the antioxidant activity and score values retrieved for different components in PARAFAC model was obtained. The possibility of using EEMs-PARAFAC to evaluate antioxidant activity of hydrophilic and lipophilic compounds in these samples was examined, obtaining good results in accordance with the Folin-Ciocalteu and TEAC assays.Publicación Analytical technique and chemometrics approaches in authenticating and identifying adulteration of paprika powder using fingerprints: a review.(Elsevier, 2022) Durán Merás, Isabel; Muñoz de la Peña, Arsenio; Galeano Díaz, Teresa; Monago Maraña, OlgaPaprika powder authentication has gained interest in recent decades along with increases in its consumption. There are different Protected Designation of Origins (PDOs) around the world, some of them are from Spain, and it is important to assure the quality parameters that they offer and to provide a guaranty about their quality and authentication. This review covers the latest advances concerning the targeted and untargeted methodologies. These methodologies have been developed to ensure paprika powder authenticity, corroborating that it belongs or not to a certain PDO and that it complies with the regulations and legal standards for its consumption, as well as detection of possible adulterations, mainly with Sudan dyes, which are illegal colorants. Differences between spectroscopic and non-spectroscopic methods have been emphasized. As observed from the literature, paprika powder has not been extensively studied, but the number of papers has been increasing in recent years.Publicación Quantification of soluble solids and individual sugars in apples by Raman spectroscopy: A feasibility study(Elsevier, 2021-06-08) Afseth, Nils Kristian; Knutsen, Svein Halvor; Wubshet, Sileshi Gizachew; Wold, Jens Petter; Monago Maraña, OlgaThis study reports the feasibility of using Raman spectroscopy for quantification of soluble solids and individual sugars in apples. Six different commercial apple varieties were measured by Raman spectroscopy at three different steps: 1) Intact apples with skin, 2) apples without skin and 3) juices obtained from apples. Results indicated that it is possible to measure Raman signals to a depth of 8 mm into the apple with a wide area Raman probe. Multivariate calibration models were established to evaluate how well Raman spectra can be used to estimate the quality parameters SSC (%), total sugars, glucose, fructose and sucrose. Estimation accuracy for SSC was comparable with what is achievable with near-infrared spectroscopy: Root mean square error of cross-validation (RMSECV) = 0.66, 0.46 and 0.72 % and coefficients of determination (R2) = 0.70, 0.85 and 0.63 for intact apples, apples without skin and juices, respectively. Sucrose and glucose were well estimated with RMSECV of 2.8, 1.9, 2.1 mg/mL for glucose and 5.8, 3.9 and 3.7 mg/mL for sucrose, for the three sample cases, respectively. Coefficient of determination was higher than 0.82 for all models. Regression coefficients for all calibration models highlighted identifiable Raman bands that could be related to the target sugars.Publicación Determination of Quercetin and Luteolin in Paprika Samples by Voltammetry and Partial Least Squares Calibration(Wiley, 2017-09-19) Chamizo González, Francisco; Galeano Díaz, Teresa; Muñoz de la Peña, Arsenio; Monago Maraña, OlgaQuercetin and luteolin are flavonoids with beneficious properties, which are present in paprika. In this work, both have been determined in paprika by using electrochemistry combined with chemometrics. The electrochemical oxidation mechanisms of both analytes have been studied through sampled direct current (DC) voltammetry, differential pulse voltammetry (DPV) and Square Wave Voltammetry (SWV), making use of a glassy carbon electrode. The final technique selected for the quantification was DPV due to its high repeatability with respect SWV. The chemical variables and the instrumental parameters were optimized and the final conditions employed were ethanol: water (20 : 80), 0.75 mol dm−3 of HCl, and a pulse amplitude of 50 mV. Due to the facts that oxidation potential of both analytes were quite similar, their DPV peaks were overlapped, and also because the analytes interaction during the electrochemical process causes a non-additivity of the signals, they could not be quantified separately by direct measurement of peak intensity. For this reason, a chemometric algorithm was applied (partial least squares (PLS) regression in its modality PLS-2). In the case of validation samples, appropriate sets of calibration and validation were built and good results were obtained. This methodology was applied to real paprika samples and the results were similar to those obtained with a HPLC method previously reported.Publicación Isocratic LC–DAD–FLD method for the determination of flavonoids in paprika samples by using a rapid resolution column and post-column pH change(Elsevier, 2016-05-15) Galeano Díaz , Teresa; Muñoz de la Peña, Arsenio; Monago Maraña, OlgaThe determination of flavonoid compounds in paprika samples has been performed by liquid chromatography in series diode array and fluorescence detection (LC–DAD–FLD), by means of a pH change to basic medium just before FLD detection. The validation of the method was performed through the establishment of the external standard calibration curves and the analytical figures of merit. Limits of detection ranging from 0.006 to 0.02 mg L−1 and 0.007 to 0.09 mg L−1 were achieved using DAD and FLD detection, respectively. The experimental conditions to carry out the hydrolysis procedure to obtain flavonoid aglycones from flavonoid glycosides have been optimized applying an experimental design and the response surface methodology. The final conditions selected were 2.5 M HCl during 45 min at 85 °C. The repeatability of this procedure was assayed and relative standard deviation (RSD) values for concentration of quercetin and luteolin compounds were lower than 2%. The quantification of quercetin, luteolin and kaempferol compounds was carried out in less than 6 min in paprika samples by means of the external standard calibration. The analytes were extracted with methanol and the extracts were previously subjected to a cleanup procedure to extend the use of the chromatographic column.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, Agustín3D-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 Four- and five-way excitation-emission luminescence-based data acquisition and modeling for analytical applications. A review(Elsevier, 2019-11-20) Alcaraz, Mirta R.; Goicoechea, Héctor C.; Muñoz de la Peña, Arsenio; Monago Maraña, OlgaThe latest advances in both theory and experimental procedures on third-order/four-way and fourth-order/five-way calibration methods are discussed. This report is focused on excitation–emission (fluorescence and phosphorescence) matrices generation, employing different variables as the third data mode (time retention in chromatography, pH gradient, fluorescence/phosphorescence lifetime, kinetics, or other chemical treatments). Fully capitalizing on the second-order advantage, it has been possible to develop appealing analytical applications in spite of the complexity of the data. Extraction of the significant chemical information about the system under study as well as the individual abundance of the contributing constituents after proper higher-order data decomposition has allowed to analytical researchers performing quantitative analysis of complex samples. The experimental works reported up to the present are introduced and discussed in order to illustrate concepts. Throughout this work, the analytical benefits achieved by modeling third- and fourth-order data are exposed, attempting to contribute to the ongoing debate in the chemometric community regarding the existence and the true nature of the third-order advantage.
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