1H–NMR fingerprinting and supervised pattern recognition to evaluate the stability of virgin olive oil during storage

Metabolomic fingerprinting of virgin olive oil (VOO) by 1H NMR spectroscopy was used to study its stability during storage simulating normal shelf life conditions during its commercialization. A representative set of VOOs covering the full range of possible chemical compositions were exposed to light (500 lux for 12 h/day) at 25 °C for 12 months or stored in the dark at 25 °C, 30 °C and 35 °C for 24 months. Multivariate data analysis of the 1H NMR spectra of the oil samples provided classification models to evaluate VOO freshness and to verify the light exposure of the VOO during storage, as well as regression models to determine VOO storage time and tentatively the best before date of a fresh VOO. These predictive models disclosed the chemical compounds responsible for the compositional changes in VOO due to hydrolytic and oxidative degradation taking place during its storage, and confirmed that light and increasing temperature enhance these processes. The presence of characteristic resonances of hydroperoxides (primary oxidation products) and the decrease of 1H signals assigned to phenolic compounds, mainly secoiridoid derivatives, and other minor compounds such as fatty acids, squalene and native (E)-2-hexenal present in fresh VOO revealed its oxidative degradation. Further, the emergence of low intensity 1H signals of saturated aldehydes meant that the secondary oxidation process has started at a low rate and yield. Moreover, the decrease of the 1H signals of triacylglycerides and sn-1,2-diacylglycerides, and the increase of sn-1,3-diacylglycerides indicated that hydrolytic degradation of VOO and diacylglyceride isomerisation was occurring. 1H NMR fingerprint of VOO together with pattern recognition techniques afford relevant information to assess the quality of VOOs taking into consideration legal, sensory and health-promoting aspects.Fil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Biología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Gallo, Blanca. Universidad del País Vasco; EspañaFil: Collado, María Isabel. Universidad del País Vasco; EspañaFil: Sasía Arriba, Andrea. Universidad del País Vasco; EspañaFil: Viacava, Gabriela Elena. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Departamento de Ingeniería Química. Grupo de Investigación en Ingeniería en Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: García González, Diego Luis. Universidad Pablo de Olavide; EspañaFil: Gallina Toschi, Tullia. Universidad de Bologna; ItaliaFil: Servili, Maurizio. Università di Perugia; ItaliaFil: Berrueta, Luis Ángel. Universidad del País Vasco; Españ

1H–NMR fingerprinting and supervised pattern recognition to evaluate the stability of virgin olive oil during storage

Metabolomic fingerprinting of virgin olive oil (VOO) by 1H NMR spectroscopy was used to study its stability during storage simulating normal shelf life conditions during its commercialization. A representative set of VOOs covering the full range of possible chemical compositions were exposed to light (500 lux for 12 h/day) at 25 °C for 12 months or stored in the dark at 25 °C, 30 °C and 35 °C for 24 months. Multivariate data analysis of the 1H NMR spectra of the oil samples provided classification models to evaluate VOO freshness and to verify the light exposure of the VOO during storage, as well as regression models to determine VOO storage time and tentatively the best before date of a fresh VOO. These predictive models disclosed the chemical compounds responsible for the compositional changes in VOO due to hydrolytic and oxidative degradation taking place during its storage, and confirmed that light and increasing temperature enhance these processes. The presence of characteristic resonances of hydroperoxides (primary oxidation products) and the decrease of 1H signals assigned to phenolic compounds, mainly secoiridoid derivatives, and other minor compounds such as fatty acids, squalene and native (E)-2-hexenal present in fresh VOO revealed its oxidative degradation. Further, the emergence of low intensity 1H signals of saturated aldehydes meant that the secondary oxidation process has started at a low rate and yield. Moreover, the decrease of the 1H signals of triacylglycerides and sn-1,2-diacylglycerides, and the increase of sn-1,3-diacylglycerides indicated that hydrolytic degradation of VOO and diacylglyceride isomerisation was occurring. 1H NMR fingerprint of VOO together with pattern recognition techniques afford relevant information to assess the quality of VOOs taking into consideration legal, sensory and health-promoting aspects.This work was supported by the European Commission within the Horizon 2020 Programme [grant agreement No. 635690, 2014–2020], and developed in the framework of the project OLEUM “Advanced solutions for assuring authenticity and quality of olive oil at global scale”. The information contained in this article reflects the authors’views; the European Commission is not liable for any use of the information contained herein

Productos Naturales en alimentos, bebidas y plantas

The chemical analysis of food and beverages has a huge interest in food science in order to develop deep knowledge of natural products, which can lead to an improvement of nutritional quality and manufacturing methods, as well as the detection of geographical origins, bad practices, adulterations and frauds.Polyphenols are a relevant group of natural products which are widely found in the Plant Kingdom. Due to their antioxidant, antimicrobial and antiparasitic properties these compounds have attracted attention for their many benefits for human health (e.g. cardiovascular diseases, cancer...), and have also been associated with the development of biotic resistance in plants. In addition, they are a key element in explaining some food properties, such as flavour, bitterness, astringency, aroma and colour.Los polifenoles son un grupo muy importante de productos naturales debido a su ubicuidad en el reino vegetal y su interés para explicar muchas de las propiedades de los alimentos, tales como el amargor, la astringencia, el aroma y el color, además de sus muchos efectos beneficiosos para la salud humana, debidos sobre todo a su gran potencial antioxidante.Fil: Gallo, Blanca. Universidad del País Vasco; EspañaFil: Berrueta, Luis Ángel. Universidad del País Vasco; EspañaFil: Sasía Arriba, Andrea. Universidad del País Vasco; EspañaFil: Asensio Regalado, Carlos. Universidad del País Vasco; EspañaFil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente; ArgentinaZientzia eta Teknologia Fakultateko VII. Ikerkuntza Jardunaldiak; VII Jornadas de Investigación de la Facultad de Ciencia y TecnologíaEspañaUniversidad del País VascoEuskal Herriko Unibertsitate

Effect of climate change on the polyphenolic composition of the main varieties of grape from La Rioja (Spain) and new oenological strategies to correct these effects on the quality of red wine

Even though grapes grow all around the planet those aimed for high quality wine production occur in areas with very specific climate conditions. Moreover, each individual variety of grape requires conditions that are even more particular. Thus, any change on the climate or meteorological patterns can affect the chemistry of the grape and the final quality of wine. Recent studies have explored the impact of climate change on the worldwide production of grape, and some highlight an advance on the vintage date associated with a temperature increase, this being for instance, 18-21 days in the South of France from 1940 to 2000. Regarding the chemical composition of wine, anthocyanins and condensed tannins are the main type of polyphenolic compounds found in red wine. Anthocyanins are the main pigments of red grapes whereas tannins play an important role on the astringency and bitterness of wine. During wine making process, both types of compounds undergo chemical transformations leading to more stable polymeric pigments. The mechanisms of these reactions and the structures of these derivative pigments have been a recurrent topic of study. With the advances on the analytical techniques, some of these structures have been elucidated, discovering products of the direct and indirect condensation of anthocyanins and tannins. Additionally, anthocyanins have been found to react with other minor components present in wine, yielding a new class of compounds called pyranoanthocyanins and producing changes in the hue of the wine [3]. A better knowledge of the formation kinetics and evolution of these pigments during wine production will allow the producer to adapt the oenological practice to control and optimise the final quality of red wine. This work is aimed towards the study of climate influence on the polyphenolic composition of must and wine from Tempranillo grape cultivar, the main variety of grape in La Rioja (Spain), and its evolution during wine production.Fil: Asensio-Regalado, Carlos. Universidad del País Vasco; EspañaFil: Sasía-Arriba, Andrea. Universidad del País Vasco; EspañaFil: Poliero, Aimará Ayelen. Universidad del País Vasco; EspañaFil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente; Argentina. Universidad Nacional de Mar del Plata, Facultad de Ciencias Exactas y Naturales, Centro de Investigación en Abejas Sociales (CIAS); ArgentinaFil: Gallo, Blanca. Universidad del País Vasco; EspañaFil: Berrueta, Luis Ángel. Universidad del País Vasco; EspañaXXXth International Conference on PolyphenolsTurkuFinlandiaGroupe Polyphénols and University of Turk

Untargeted Metabolomic Liquid Chromatography High-Resolution Mass Spectrometry Fingerprinting of Apple Cultivars for the Identification of Biomarkers Related to Resistance to Rosy Apple Aphid

Liquid chromatography high-resolution mass spectrometry fingerprinting together with pattern recognition techniques was used to determine the metabolites involved in the susceptibility of apple cultivars to rosy apple aphid (RAA). Preprocessing of ultra-high-performance liquid chromatography coupled to electrospray ionization and quadrupole time-of-flight mass spectrometry raw data of resistant and susceptible apple cultivars was carried out with XCMS and CAMERA packages. Univariate statistical tools and multivariate data analysis highlighted significant different profiles of the apple metabolomes according to their tolerance to RAA. Optimized and cross-validated Partial least squares discriminant analysis and orthogonal projections to latent structures discriminant analysis models confirmed trans-4-caffeoylquinic acid and 4-p-coumaroylquinic acid as biomarkers for the identification of resistant and susceptible apple cultivars to RAA and disclosed that only hydroxycinnamic acids are involved in the disease susceptibility of cultivars. In this sense, the final steps of the biosynthesis of caffeoylquinic acid (CQA) and p-coumaroylquinic acid (p-CoQA) become decisive because the isomerization of 5-CQA to 4-CQA is favored in resistant cultivars, whereas the isomerization of 5-p-CoQA to 4-p-CoQA is favored in susceptible cultivars.Fil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones en Sanidad Producción y Ambiente. - Comisión de Investigaciones Científicas de la Provincia de Buenos Aires. Instituto de Investigaciones en Sanidad Producción y Ambiente; ArgentinaFil: Berrueta, Luis A.. Universidad del País Vasco; EspañaFil: Abad García, Beatriz. Universidad del País Vasco; EspañaFil: Sasía Arriba, Andrea. Universidad del País Vasco; EspañaFil: Asensio Regalado, Carlos. Universidad del País Vasco; EspañaFil: Dapena, Enrique. No especifíca;Fil: Gallo, Blanca. Universidad del País Vasco; Españ

Untargeted metabolomic LC-MS fingerprinting of apple cultivars for the identification of biomarkers related to resistance to rosy apple aphid

Phenolic compounds may play important roles in plant responses to biotic-stress and in resistance mechanisms. In a previous work, we demonstrated the correlation between phenolic composition of apple cultivars and their tolerance to rosy apple aphid (RAA), Dysaphis plantaginea, a key pest of apple. The study was performed on a full-sib family produced at SERIDA, derived from a crossing between the local apple cultivar ?Meana? and the resistant cultivar ?Florina?. It consisted in the determination of the concentrations of individual flavan 3 ols, hydroxycinnamic acids, dihydrochalcones and flavonols by UHPLC-DAD present in the two parents and 154 descendants; and their resistance to RAA was determined after aphid inoculation in greenhouse. A relationship between the concentration of three caffeoylquinic acid isomers (4-CQA, 1-CQA and 3-CQA) and 4-p-coumaroylquinic acid (4-pCoQA) and the resistance to RAA was found by pattern recognition techniques. Cultivar resistance to RAA was concluded to be related with the phenylpropanoid pathway; the isomerisations being the key metabolic reactions for a cultivar to be resistant or susceptible to RAA.In the present work, the phenolic profiles of the same set of samples were analysed by UHPLC-ESI(+)-QTOF/MS to use an untargeted metabolomic approach to identify biomarkers related to resistance to RAA. Apple phenolic fingerprints and their resistance to RAA were submitted to multivariate data analysis by Principal Component Analysis, Hierarchical Clustering Analysis, Partial Least Square-Discriminant Analysis (PLSDA) and Orthogonal-PLSDA (O-PLSDA), which disclosed that the main features related to resistant cultivars were due to 4-CQA, and those related to susceptible cultivars to 5-pCoQA. These results agreed with previous ones since both phenolics are involved in the isomerisation reactions mentioned above.Fil: Sasía Arriba, Andrea. Universidad del País Vasco; EspañaFil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente; ArgentinaFil: Asensio Regalado, Carlos. Universidad del País Vasco; EspañaFil: Poliero, Aimará Ayelen. Universidad Nacional de Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Producción, Sanidad y Ambiente; ArgentinaFil: Abad García, Beatriz. Universidad del País Vasco; EspañaFil: Dapena, Enrique. No especifíca;Fil: Gallo, Blanca. Universidad del País Vasco; EspañaFil: Berrueta, Luis Ángel. Universidad del País Vasco; EspañaXXX International Conference on PolyphenolsTurkuFinlandiaInternational Association of Groupe PolyphenolsUniversity of Turk

Relationship between hydroxycinnamic acids and the resistance of apple cultivars to rosy apple aphid

The phenolic profiles of apple cultivars from the SERIDA Asturian cider apple breeding program, including parents and progenies, were determined by ultrahigh-performance liquid chromatography-diode array detector-electrospray ionization-quadrupole time of flight/mass spectrometer in order to study the relationship between phenols and the resistance of apple tree cultivars to rosy apple aphid (RAA). A pattern recognition technique named partial least square discriminant analysis (PLS-DA) was used to classify apple cultivars based on resistance to RAA, resistant and susceptible, reaching scores with accuracy higher than 97% and 91% respectively. Hydroxycinnamic acids, particularly 4-caffeoylquinic acid (4-CQA) and 4-p-coumaroylquinic acid (4-pCoQA), were identified as the major player in RAA resistance by the PLS-DA model. Indeed, the isomerisation 5-CQA → 4-CQA is favoured in resistant cultivars, whereas the isomerisation 5-pCoQA → 4-pCoQA is favoured in susceptible cultivars. As a result, resistant cultivars accumulate higher amounts of 4-CQA than susceptible ones, and the opposite occurs for 4-pCoQA. Also, minor isomerisations of 5-CQA to 1-CQA or 3-CQA show opposite behaviour for resistant and susceptible cultivars. Cultivar resistance to RAA is concluded to be related with the phenylpropanoid pathway, the isomerisation reactions being the key metabolic reaction for a cultivar to be resistant or susceptible to RAA.Fil: Berrueta, Luis A.. Universidad del País Vasco; EspañaFil: Sasía-Arriba, Andrea. Universidad del País Vasco; EspañaFil: Miñarro, Marcos. Serida; EspañaFil: Antón, María J.. Serida; EspañaFil: Alonso Salces, Rosa Maria. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Biología. Laboratorio de Artrópodos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Micheletti, Diego. Instituto Agrario San Michele all'Adige Fondazione Edmund Mach; ItaliaFil: Gallo, Blanca. Universidad del País Vasco; EspañaFil: Dapena, Enrique. Serida; Españ