Predicción de la frescura del aceite de oliva virgen extra durante el almacenamiento mediante espectroscopía de fluorescencia

Virgin olive oil quality relates to flavor and unique health benefits. Some of these properties are at the most desirable level when the oil is just extracted, since it is not a product that improves with age. On the contrary, the concentrations of many compounds change during its shelf-life. These changes reveal the aging of the oil but do not necessarily mean decay in sensory properties, so in some cases an aged oil from healthy olives may be better qualified than a fresh one from olives affected by fermentation. The aim of this work is to analyze different methodologies proposed for assessing the quality of virgin olive oil with implications in freshness and aging of the oil, and to highlight the possibilities of rapid spectrofluorimetric techniques for assessing oil freshness by checking the evolution of pigments during storage. The observed change in the selected spectral features and mathematical modelling over time was compared with the accepted model for predicting the amount of pyropheophytin a, which is based on isokinetic studies. The best regression was obtained for 655 nm (adjustedR2 = 0.91) wavelength, which matches the distinctive band of pigments. The two mathematical models described in this study highlight the usefulness of pigments in the prediction of the shelf-life of extra virgin olive oil.La calidad del aceite de oliva virgen está relacionada con su flavor y sus beneficios únicos para la salud. Algunas de estas propiedades se encuentran en el nivel más deseable cuando el aceite está recién extraído, ya que no es un producto que mejore con el tiempo. Por el contrario, las concentraciones de muchos compuestos cambian a lo largo de la vida útil. Estos cambios revelan el envejecimiento del aceite, pero no implican necesariamente la alteración de las propiedades sensoriales, por lo que en algunos casos un aceite envejecido procedente de aceitunas sanas puede presentar mejor calidad que uno fresco procedente de aceitunas afectadas por procesos de fermentación. El objetivo de este trabajo es estudiar diferentes metodologías propuestas para evaluar la calidad del aceite de oliva virgen con implicaciones en la frescura y el envejecimiento del aceite, destacando las posibilidades de las rápidas técnicas espectrofluorométricas para evaluar la frescura del aceite verificando la evolución de los pigmentos durante el almacenamiento. El cambio observado en las características espectrales seleccionadas y su modelado matemático a lo largo del tiempo se comparó con el modelo aceptado para predecir la cantidad de pirofeofitina a, que se basa en estudios isocinéticos. Los dos modelos matemáticos descritos en este estudio pusieron de manifiesto la utilidad de los pigmentos en la predicción de la vida útil del aceite de oliva virgen extra. La mejor regresión se obtuvo para 655 nm (R2 -ajustado = 0,91), longitud de onda que coincide con la banda distintiva de pigmentos.Secretaría de Estado de Investigación, Desarrollo e Innovación de España-AGL2015-69320-

Predicción de la frescura del aceite de oliva virgen extra durante el almacenamiento mediante espectroscopía de fluorescencia

Virgin olive oil quality relates to flavor and unique health benefits. Some of these properties are at the most desirable level when the oil is just extracted, since it is not a product that improves with age. On the contrary, the concentrations of many compounds change during its shelf-life. These changes reveal the aging of the oil but do not necessarily mean decay in sensory properties, so in some cases an aged oil from healthy olives may be better qualified than a fresh one from olives affected by fermentation. The aim of this work is to analyze different methodologies proposed for assessing the quality of virgin olive oil with implications in freshness and aging of the oil, and to highlight the possibilities of rapid spectrofluorimetric techniques for assessing oil freshness by checking the evolution of pigments during storage. The observed change in the selected spectral features and mathematical modelling over time was compared with the accepted model for predicting the amount of pyropheophytin a, which is based on isokinetic studies. The best regression was obtained for 655 nm (adjustedR2 = 0.91) wavelength, which matches the distinctive band of pigments. The two mathematical models described in this study highlight the usefulness of pigments in the prediction of the shelf-life of extra virgin olive oil.La calidad del aceite de oliva virgen está relacionada con su flavor y sus beneficios únicos para la salud. Algunas de estas propiedades se encuentran en el nivel más deseable cuando el aceite está recién extraído, ya que no es un producto que mejore con el tiempo. Por el contrario, las concentraciones de muchos compuestos cambian a lo largo de la vida útil. Estos cambios revelan el envejecimiento del aceite, pero no implican necesariamente la alteración de las propiedades sensoriales, por lo que en algunos casos un aceite envejecido procedente de aceitunas sanas puede presentar mejor calidad que uno fresco procedente de aceitunas afectadas por procesos de fermentación. El objetivo de este trabajo es estudiar diferentes metodologías propuestas para evaluar la calidad del aceite de oliva virgen con implicaciones en la frescura y el envejecimiento del aceite, destacando las posibilidades de las rápidas técnicas espectrofluorométricas para evaluar la frescura del aceite verificando la evolución de los pigmentos durante el almacenamiento. El cambio observado en las características espectrales seleccionadas y su modelado matemático a lo largo del tiempo se comparó con el modelo aceptado para predecir la cantidad de pirofeofitina a, que se basa en estudios isocinéticos. Los dos modelos matemáticos descritos en este estudio pusieron de manifiesto la utilidad de los pigmentos en la predicción de la vida útil del aceite de oliva virgen extra. La mejor regresión se obtuvo para 655 nm (R2 -ajustado = 0,91), longitud de onda que coincide con la banda distintiva de pigmentos.Secretaría de Estado de Investigación, Desarrollo e Innovación de España-AGL2015-69320-

Valorización energética de la biomasa : aplicación en industrias del sector agroalimentario

La utilización de la biomasa proveniente del sector agroalimentario como una fuente de energía renovable es de gran interés en la actualidad. Ésta puede generar energía, a través de procesos tanto termoquímicos como bioquímicos, susceptible de utilizarse en forma de calor, energía mecánica o electricidad, y en diferentes estados de agregación: sólida, líquida o gas. La Digestión Anaerobia de vertidos de destilerías vínicas es un ejemplo idóneo de los procesos bioquímicos de conversión de la biomasa para obtener energía, ya que la vinaza se genera en el propio proceso de obtención del alcohol etílico (destilación de vinos y subproductos de la vinificación) producido por fermentación de una disolución azucarada y el metano se genera en la digestión anaerobia del residuo de la destilación. En este trabajo se estudia el funcionamiento y operación de diferentes tecnologías anaerobias susceptibles de ser utilizadas para la degradación de vertidos de destilerías vínicas (vinazas de vino) en condiciones anaerobias termofílicas (55°C), estableciéndose una comparación entre procesos con biomasa en suspensión y sistemas con biomasa adherida de tipo filtro anaerobio. En este último caso, además, se comparan diferentes tipos de materiales soportes y se analiza el efecto de la tasa de recirculación sobre el proceso.____________________________________Nowadays, the use of food industry biomass as a resource of renewable energy is a very interesting management alternative. Biomass can be converted to energy via thermal, biochemical and mechanical processes. This energy can be used like heat, mechanic o electric energies, and in different aggregation states (solid, liquid or gaseous). Anaerobic digestion of wine distilleries wastewater (vinasses) is a suitable example of biochemical conversion process of biomass to obtain energy. Vinasses are generated in the obtaining of ethylic alcohol on wine and wine-subproducts distillation process. This alcohol is previously generated in the biological fermentation of sugars from must. Subsequently, the biogas, mainly methane, can be obtained from anaerobic digestion of the residue of alcohol distillation, the vinasses. This work presents the main operational conditions of different anaerobic technologies used for anaerobic digestion of wine distilleries wastewater (vinasses) in the thermophilic range of temperature (55ºC). This study makes the comparison between technologies that used suspended biomass and fixed-film biorreactors (anaerobic filters). In the anaerobic filter technology there is a comparison between different support media and different recirculation rate regimes and its influence in the process

Theoretical modeling of electronic excitations of gas-phase and solvated TiO2 nanoclusters and nanoparticles of interest in photocatalysis

The optical absorption spectra of (TiO2)n, nanoclusters (n = 1-20) and nanoparticles (n = 35, 84) have been calculated from the frequency-dependent dielectric function in the independent particle approximation under the framework of density functional theory. The PBE generalized gradient approach based functional, the so-called PBE+U method and the PBE0 and PBEx hybrid functionals containing 25% and 12.5% of nonlocal Fock exchange, respectively have been used. The simulated spectra have been obtained in the gas phase and in water on previously PBE0 optimized atomic structures. The effect of the solvent has been accounted for by using an implicit water solvation model. For the smallest nanoclusters, the spectra show discrete peaks, whereas for the largest nanoclusters and for the nanoparticles they resemble a continuum absorption band. In the gas phase and for a given density functional, the onset of the absorption (optical gap, Ogap) remains relatively constant for all nanoparticle sizes although it increases with the percentage of nonlocal Fock exchange, as expected. For all tested functionals, the tendency of Ogap in water is very similar to that observed in the gas phase with an almost constant upshift. For comparison, the optical gap has also been calculated at the TD-DFT level with the PBEx functional in the gas phase and in water. Both approaches agree reasonably well although the TD-DFT gap values are lower than those derived from the dielectric-function. Overall, the position of the spectral maxima and the width of the spectra are relatively constant and independent of particle size which may have implications in the understanding of photocatalysis by TiO2

Electronic properties of realistic anatase TiO2 nanoparticles from G(0)W(0) calculations on a Gaussian and plane waves scheme

The electronic properties of realistic (TiO2)n nanoparticles (NPs) with cuboctahedral and bipyramidal morphologies are investigated within the many-body perturbation theory (MBPT) G0W0 approximation using PBE and hybrid PBEx (12.5% Fock contribution) functionals as starting points. The use of a Gaussian and plane waves (GPW) scheme reduces the usual O4 computational time required in this type of calculation close to O3 and thus allows considering explicitly NPs with n up to 165. The analysis of the Kohn-Sham energy orbitals and quasiparticle (QP) energies shows that the optical energy gap (Ogap), the electronic energy gap (Egap), and the exciton binding energy (ΔEex) values decrease with increasing TiO2 NP size, in agreement with previous work. However, while bipyramidal NPs appear to reach the scalable regime already for n = 84, cuboctahedral NPs reach this regime only above n = 151. Relevant correlations are found and reported that will allow one to predict these electronic properties at the G0W0 level in even much larger NPs where these calculations are unaffordable. The present work provides a feasible and practical way to approach the electronic properties of rather large TiO2 NPs and thus constitutes a further step in the study of realistic nanoparticles of semiconducting oxides

Theoretical calculations of the effect of nitrogen substitution on the structural, vibrational, and electronic properties of wolframite-type ScTaO4 at ambient conditions

In this study, the effect of nitrogen substitution in wolframite-type ScTaO4 was investigated using density- functional theory calculations. First, structural and mechanical properties, as well as the dynamical stability of ScTaO4 were examined deeply for the ambient-pressure structure. Subsequently, we studied how lattice vibrations are affected by hydrostatic pressure and determined the elastic moduli of ScTaO4. The results of our study show that the monoclinic structure of ScTaO4 is rigid and non-compressible. In addition, band- structure calculations show that ScTaO4 has a wide direct band-gap of 4.04 eV, which in turn leads to a possible tuning of electronic properties. We have found that this task can be conducted by partially substi- tuting oxygen atoms in the unit cell with nitrogen atoms. Both band-structure calculations and charge- density analyses revealed a narrowing in the band gap caused by the presence of nitrogen atoms, which act as a shallow acceptor state, resulting in weak repulsive interactions and structural distortions in both Sc and Ta coordination polyhedra; reducing the crystal symmetry from monoclinic to triclinic

An empirical, yet practical way to predict the band gap in solids by using density functional band structure calculations

Band structure calculations based on density functional theory (DFT) with local or gradient-corrected exchange-correlation potentials are known to severely underestimate the band gap of semiconducting and insulating materials. Alternative approaches have been proposed: from semiempirical setups, such as the so-called DFT +U, to hybrid density functionals using a fraction of nonlocal Fock exchange, to modifications of semilocal density functionals. However, the resulting methods appear to be material dependent and lack theoretical rigor. The rigorous many-body perturbation theory based on GW methods provides accurate results but at a very high computational cost. Hereby, we show that a linear correlation between the electronic band gaps obtained from standard DFT and GW approaches exists for most materials and argue that (1) this is a strong indication that the problem of predicting band gaps from standard DFT calculation arises from the assignment of a physical meaning to the Kohn-Sham energy levels rather than from intrinsic errors of the DFT methods and (2) it provides a practical way to obtain GW-like quality results from standard DFT calculations. The latter will be especially useful for systems where the unit cell involves a large number of atoms as in the case of doped or defect-containing materials for which GW calculations become unfeasible

Use of internal boundary conditions for levees representation: application to river flood management

River floods can be simulated with the 2D shallow water system of equations using finite volume methods, where the terrain is discretized in cells that form the computational mesh. Usually a proper treatment of wet/dry fronts is required. River levees can be modelled as part of the topography by means of sufficiently small cells of higher elevation than the rest of the bed level in locally refined meshes. This procedure is associated with a large computational time since the time step depends directly on the cell size. The alternative proposed in this work includes the levees as internal boundary conditions in the 2D numerical scheme. In particular, levees have been defined by a weir law that, depending on the relative values of water surface levels on both sides, can formulate the discharge for different situations (i.e. free flow and submerged flow). In addition, having identified numerical difficulties in cases of low discharge under free flow conditions, a novel procedure to avoid oscillations has been developed and called volume transport method. The validation and comparison between methods has been carried out with benchmark test cases and, in addition, with a real flood event in the Ebro River (Spain)

Morphology of TiO2 nanoparticles as fingerprint for the transient absorption spectra: implications for photocatalysis

Understanding the relationship between structural properties and the character of the charged carriers in photoactive TiO2 nanoparticles is fundamental to improving their photocatalytic activity. Transient absorption spectroscopy (TAS) is often used to explore the character of the charge carriers, but carrying out experiments on well-defined nanoparticles with a given morphology and selected size is extremely difficult. Here, hybrid time-dependent density functional theory based calculations carried out for realistic TiO2 nanoparticles (NPs) with bipyramidal, truncated, and spherical morphologies reveal that the electron-trapped carriers are quite sensitive to the NP morphology. In particular, these carriers are shallowly trapped in faceted NPs whereas they are deeply trapped in those exhibiting a spherical morphology. In addition, the simulated absorption spectra can be compared directly to experimental ones obtained by TAS, thus allowing additional information to be provided regarding the morphology of the TiO2 NPs in a given sample. Note that although the present study focuses on TiO2 nanoparticles, it can be easily extended to other photoactive materials such as ZnO or WO3 NPs thus allowing the extraction of information regarding the relationship between the NP morphology and the nature of the low-lying excited states

Investigating the character of excited states in TiO2 nanoparticles from topological descriptors: implications for photocatalysis

Titanium dioxide (TiO2) nanoclusters (NCs) and nanoparticles (NPs) have been the focus of intense research in recent years since they play a prominent role in photocatalysis. In particular, the properties of their excited states determine the photocatalytic activity. Among the requirements for photocatalytic activity, low excitation energy and large separation of the charge carriers are crucial. While information regarding the first is straightforward from either experiment or theory, the information regarding the second is scarce or missing. In the present work we fill this gap through a topological analysis of the first singlet excited state of a series of TiO2 NCs, and anatase and rutile derived NPs containing up to 495 atoms. The excited states of all these systems in vacuo have been obtained from time-dependent density functional theory (TDDFT) calculations using hybrid functionals and the influence of water was taken into account through a continuum model. Three different topological descriptors based on the attachment/detachment one-electron charge density, are scrutinized: (i) charge transfer degree, (ii) charge density overlap, and (iii) distance between centroids of charge. The present analysis shows that the charge separation in the excited state strongly depends on the NP size and shape. The character of the electronic excitations, as arising from the analysis of the canonical Kohn-Sham molecular orbitals (MOs) or from natural transition orbitals (NTOs), is also investigated. The understanding and prediction of charge transfer and recombination in TiO2 nanostructures may have implications in the rational design of these systems to boost their photocatalytic potential