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La exposición humana a contaminantes emergentes es una realidad cada vez más evidente. Las múltiples rutas por las que se puede producir la exposición a estos compuestos y los diferentes mecanismos de acción que pueden generar supone un punto más de complicación en las consecuencias que puede tener sobre la salud. El embarazo y el desarrollo fetal suponen una etapa especialmente sensible en la exposición a estos compuestos, debido a las posibles consecuencias que podría llegar a tener sobre la salud de la madre durante este periodo y sobre el correcto desarrollo del recién nacido. En este punto entra en juego, además, el estilo de vida de las mujeres, pudiendo suponer un riesgo adicional, ya que la exposición a algunos de estos contaminantes emergentes se puede producir a través de la alimentación o el consumo de tabaco, por ejemplo. La biomonitorización humana es una herramienta muy útil en la obtención de información sobre la exposición humana a sustancias químicas, permitiendo de este modo el desarrollo de técnicas para la protección de la salud. Esta herramienta se puede usar para poder conocer tanto los niveles de exposición individuales como los de la población general, haciendo especial incidencia en el caso de poblaciones vulnerables como son las mujeres embarazadas. Con estos precedentes, el objetivo principal de nuestro estudio fue la biomonitorización de contaminantes ambientales (metales y parabenos) en una cohorte de parejas de mujeres embarazadas-recién nacido residentes en Sevilla y provincia y la determinación del estado oxidativo con el fin de relacionarlo con el estado de salud y las características antropométricas de los recién nacidos y sociodemográficas de las participantes. Para abordar el estudio se llevó a cabo una búsqueda del estado del arte de los estudios de exposición a plaguicidas en poblaciones femeninas rurales y urbanas, reflejado en el capítulo 1: “Impact of Pesticide Exposure among Rural and Urban Female Population. An Overview”. A, Human exposure to emerging contaminants is an increasingly evident reality. The multiple pathways through which exposure to these compounds can occur, and the different mechanisms of action they can generate, represent an additional level of complexity in the health consequences they may have. Pregnancy and fetal development represent a particularly sensitive stage in exposure to these compounds, due to the potential health consequences for both the mother and the newborn during this period. At this point, the lifestyle of women also comes into play, potentially being an additional risk, as exposure to some of these emerging contaminants can occur through diet or tobacco consumption, for example. Human biomonitoring is a very useful tool in obtaining information about human exposure to chemical substances, thus allowing the development of techniques for health protection. This tool can be used to determine both individual exposure levels and those of the general population, with particular emphasis on vulnerable populations such as pregnant women. Against this background, the main objective of our study was the biomonitoring of environmental contaminants (metals and parabens) in a cohort of pregnant women and their newborns residing in Seville and its province, and the determination of oxidative status in order to correlate it to the health status and anthropometric characteristics of newborns and the sociodemographic characteristics of the participants. To address the study, a search for the state of the art of studies on pesticide exposure in rural and urban female populations was carried out, reflected in chapter 1: "Impact of Pesticide Exposure among Rural and Urban Female Population. An Overview". Additionally, determination of metal levels in maternal and cord blood samples was carried out, reflected in chapter 2: "Monitoring of metals and metalloids from maternal and cord blood samples in a population from Seville (Spain)", and determination of paraben levels

Background Sulforaphane (SFN) is a dietary isothiocyanate, derived from glucoraphanin, present in cruciferous vegetables belonging to the Brassica genus. It is a biologically active phytochemical that acts as a nuclear factor erythroid 2-related factor 2 (Nrf2) inducer. Thus, it has been reported to have multiple protective functions including anticancer responses and protection against a toxic agent's action. Purpose The present work systematically reviewed and synthesised the protective properties of sulforaphane against a toxic agent. This review reveals the mechanism of the action of SFN in each organ or system. Methods The PRISMA guideline was followed in this sequence: researched literature, organised retrieved documents, abstracted relevant information, assessed study quality and bias, synthesised data, and prepared a comprehensive report. Searches were conducted on Science Direct and PubMed using the keywords "Sulforaphane" AND (“protective effects” OR “protection against”). Results Reports showed that liver and the nervous system are the target organs on which attention was focused, and this might be due to the key role of oxidative stress in liver and neurodegenerative diseases. However, protective activities have also been demonstrated in the lungs, heart, immune system, kidneys, and endocrine system. SFN exerts its protective effects by activating the Nrf2 pathway, which enhances antioxidant defenses and reduces oxidative stress. It also suppresses inflammation by decreasing interleukin production. Moreover, SFN inhibits apoptosis by preventing caspase 3 cleavage and increasing Bcl2 levels. Overall, SFN demonstrates multifaceted mechanisms to counteract the adverse effects of toxic agents. Conclusion SFN has potential clinical applications as a chemoprotective agent. Nevertheless, more studies are necessary to set the safe doses of SFN in humans.

Anatoxin-a (ATX-a) is a potent neurotoxin produced by several species of cyanobacteria whose exposure can have direct consequences, including neurological disorders and death. The increasing prevalence of harmful cyanobacterial blooms makes the detection and reliable assessment of ATX-a levels essential to prevent the risk associated with public health. Therefore, the aim of this review is to compile the analytical methods developed to date for the detection and quantification of ATX-a levels alone and in mixtures with other cyanotoxins and their suitability. A classification of the analytical methods available is fundamental to make an appropriate choice according to the type of sample, the equipment available, and the required sensitivity and specificity for each specific purpose. The most widely used detection technique for the quantification of this toxin is liquid chromatography–tandem mass spectrometry (LC-MS/MS). The analytical methods reviewed herein focus mainly on water and cyanobacterial samples, so the need for validated analytical methods in more complex matrices (vegetables and fish) for the determination of ATX-a to assess dietary exposure to this toxin is evidenced. There is currently a trend towards the validation of multitoxin methods as opposed to single-ATX-a determination methods, which corresponds to the real situation of cyanotoxins’ confluence in nature.

A lo largo de la historia se ha utilizado el olor para detectar diferentes enfermedades, como es el caso de la diabetes debido a la presencia de un olor dulce y afrutado en la orina y el aliento de los pacientes. Además, se ha demostrado que algunos perros entrenados pueden identificar patologías humanas como el cáncer, por lo que se confirma la existencia de sustancias volátiles que producen olores característicos en determinadas enfermedades. En este sentido, los compuestos orgánicos volátiles (COVs) llevan años estudiándose como potenciales biomarcadores, encontrándose utilidad tanto en el diagnóstico como en el seguimiento de muchas enfermedades. La detección temprana de las enfermedades permite mejorar la calidad de vida y aumentar la tasa de supervivencia de los pacientes, por lo que es de suma importancia implementar nuevos métodos diagnósticos que superen los inconvenientes de las técnicas tradicionales y sean rápidos, confiables, no invasivos, accesibles y económicos. Por lo tanto, el objetivo principal de la presente Tesis Doctoral ha sido la búsqueda de potenciales biomarcadores volátiles, mediante el análisis de muestras biológicas no invasivas, que faciliten el diagnóstico de diferentes enfermedades o se relacionen con su progresión, empleando para su determinación la cromatografía de gases acoplada a la espectrometría de masas. Para la consecución de este objetivo se han analizado muestras de pacientes con enfermedades infecciosas y no infecciosas, organizándose esta Tesis Doctoral, por tanto, en dos grandes capítulos. Así, el primer capítulo engloba cuatro trabajos que tratan sobre la identificación de potenciales biomarcadores volátiles de microorganismos causantes de enfermedades infecciosas, utilizando para ello diferentes muestras biológicas o medio de tioglicolato. En concreto, en los estudios centrados en pacientes con tricomoniasis y otras infecciones de transmisión sexual, cabe destacar la importancia de analizar los COVs en muestras de flujo

The influence of the geographical location on the chemical composition of commercial Sauvignon Blanc wines was investigated. The assay was carried out on Sauvignon Blanc wines from three cold-climate valleys in Central Chile, Casablanca, Leyda, and San Antonio. The analyses revealed clear variations in some chemical parameters, especially in titratable acidity, which was higher in the geographical areas closest to the Pacific Ocean, such as the Leyda and San Antonio valleys. Regarding the composition of low-molecular-weight phenolic compounds, 17 compounds were found, and the results show that the Casablanca valley exhibits a greater abundance of monomeric flavanols, such as (+)-catechin, whereas the Leyda valley shows a higher abundance in flavonols and phenolic acids esterified with tartaric acid. Concerning the aromatic compound profile, the wines from the Casablanca valley showed a greater abundance of esters, C13 norisoprenoids, and some terpenes. The PLS-DA analysis revealed some differences, especially between wines from Casablanca and Leyda, demonstrating that the difference in the chemical composition of the wines was influenced by the geographical area.

Camu-camu (Myrciaria dubia) is a tropical fruit known for its content of bioactive compounds. This study aimed to evaluate physicochemically, morphologically, andsensorialpowders from camu-camu obtained by spray-drying at two inlet temperatures (150 °C and 180 °C) with three encapsulating agents (maltodextrin, whey protein and a 50:50 mixture of both) and by freeze-drying of whole fruit. The use of maltodextrin protected bet anthocyanins (cyanidin-3-glucoside (C3G) and delphinidin-3-glucoside (D3G)), but whey protein showed a better protective effect on ascorbic and malic acids. These facts were confirmed during the storage stability test, finding that relative humidity is a critical variable in preserving the bioactive compounds of camu-camu powders. The powders with the highest content of bioactive compounds were added to a yogurt and a white grape juice, and then sensory evaluated. The bioaccessibility studies in gastric and intestinal phases showed better recovery percentages of bioactive compounds in camu-camu powders (up to 60.8 %) and beverages (up to 90 %) for C3G, D3G, ascorbic acid, and malic acid than in the fruit juice. Dehydration of camu-camu (M. dubia) is a strategy to increase the bioactive compounds stability, modulate the fruit sensory properties, and improve their bioavailability after incorporation in food matrices.

Hyperspectral imaging is a well-known technique for quality control of food and agricultural products. This technique is often applied to the measurement of large and heterogeneous samples, where chemical imaging is extremely useful. In addition, when the amount of sample is limited by different factors (price, other analyses, sample production, etc.) hyperspectral imaging is an alternative to traditional spectroscopes for acquiring its spectral information. In this study, a new and specific methodology to acquire hyperspectral information from small amounts of granular samples has been developed. For this purpose, two different hyperspectral devices (400–1100 nm, 900–1700 nm) have been used. A statistical procedure has been followed to test the proposed method. In grape seed protein concentrates, NIR radiation (900–1700 nm) penetrates deeper into the sample than VisNIR radiation (400–1100 nm). Therefore, the minimum amount of sample needed to measure in the NIR range is larger than that needed to measure in the VisNIR range. Finally, different calibration models have been developed for the control of protein content in the tested samples. Standard errors of prediction obtained in external validation are similar to those reported in the literature when sample amount is not an issue (9–10 %).

Fortified wines covered by a Protected Designation of Origin (PDO) are high-quality products appreciated by consumers, whose diversity has increased in recent years, leading to an increased vulnerability to fraud. In this work, for the first time, an excitation-emission fluorescence spectroscopy method combined with two chemometric approaches was developed for the characterization and authentication of PDO fortified wines. A visual assessment of fluorescence landscapes pointed out different trends. The excitation-emission matrix (EEM) was decomposed using Parallel Factor Analysis (PARAFAC) for the extraction of potential fluorophores, or unfolded, and then, the resulting matrices were subjected to Principal Component Analysis (PCA) and Partial Least Squares-Discriminant Analysis (PLS-DA). Both approaches were able to discriminate the wine type within each PDO, the PDO within a wine type, and the production process. The proposed analytical and chemometric tools could be used as an alternative control method for a rapid screening of Spanish PDO fortified wines.

Antioxidant activity can be evaluated using cyclic voltammetry (CV). The aim of this work is to verify the efficacy of CV in evaluating the synergistic effect of bioactive compounds, such as phenolic and amino acid compounds, on antioxidant activity. Therefore, three types of model solutions were prepared: individual model solution (phenol and amino acid), (b) binary model solutions (phenol-phenol and amino acid-amino acid) and (c) mixed phenol–amino acid solutions. Electrochemical measurement conditions were optimized for phenolic compounds (pH 3.0, 1.0 g/L and 100 mV/s) and for amino acids (pH 7.0, 2.0 g/L for amino acids and 100 mV/s), and, for each solution, the functional groups responsible of the anodic and cathodic peaks were established. The peak anodic potential (Epa) and the onset potential (Eon) were two parameters of great importance. The first one was used to classify the solutions according to their antioxidant potential. In general, all the binary and mixed solutions had lower values of Epa than the corresponding individual model solution, which indicates an improvement in the antioxidant potential. The second one was used to evaluate the synergistic effects of phenolic compounds and amino acids.

In this study, an electro assisted liquid phase microextraction (EA-LPME) procedure to determine seven parabens (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and benzyl paraben) and three of their key hydroxy metabolites (4-hydroxy, 3,4-dihydroxy, and 3,4,5-trihydroxy benzoic acid) was optimised in maternal urine and amniotic fluid obtained at delivery from pregnant women. The samples were analysed by ultra-high-performance liquid chromatography coupled with electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS/MS). PHBs and their metabolites were extracted from a pH 4 donor solution (10 mL) into a pH 13 acceptor solution (50 µL) using 1-octanol as the supported liquid membrane (SLM) and 30 V for 40 min at 400 rpm. Under optimal operational conditions, enrichment factors between 10 and 90 were achieved, and low quantitation limits within 0.022–0.20ng mL⁻¹ and 0.025–0.18 ng mL⁻¹, were obtained for amniotic fluid and urine, respectively. The proposed analytical procedure was satisfactorily applied for the determination of target compounds in seven paired maternal urine and amniotic fluid samples to evaluate the possible placental transfer of these compounds from mothers to babies.

The availability of pure individual betalains in sufficient quantities which permit deeper understanding is still a challenge. This study investigates the high-yielding semisynthesis of betaxanthins using betalamic acid from a natural source (Opuntia dillenii), followed by condensation with ʟ-amino acids and further purification. Moreover, the color stability of the four synthesized individual betaxanthins, namely proline (ʟ-ProBX), alanine (ʟ-AlaBX), leucine (ʟ-LeuBX), and phenylalanine (ʟ-PheBX) betaxanthins, was investigated at different pHs. Their relative contribution to free radical scavenging was also scrutinized by TEAC and DPPH. ʟ-AlaBX and ʟ-LeuBx showed a significantly (p < 0.05) higher antioxidant activity, whereas ʟ-ProBX was the most resistant to the hydrolysis of betaxanthin and hence the least susceptible to color change. The color stability was strongly influenced by pH, with the color of ʟ-ProBX, ʟ-LeuBX, and ʟ-AlaBX at pH 6 being more stable, probably due to the easier hydrolysis under acid conditions. The semisynthesis and purification allowed us to have available remarkable quantities of pure individual betaxanthins of Opuntia dillenii for the first time, and to establish their color properties and antioxidant capacity. This study could be a step forward in the development of the best natural food colorant formulation, based on the betalain structure, which is of special interest in food technology.

This study aimed at optimizing the accumulation of phytoene in Chlorella sorokiniana by using norflurazon and investigating the capacity of green and traditional solvents to extract carotenoids by ultrasound-assisted extraction with and without previous milling. Phytoene-rich first described C. sorokiniana biomass was used, both fresh, freeze-dried, and encapsulated. The ideal dose of norflurazon (1 µg/mL) was selected to block the carotenoid pathway at the level of phytoene desaturase and induce the accumulation of phytoene in C. sorokiniana. A mill pre-treatment allowed a higher recovery of carotenoids compared to non-milled samples, in both the freeze-dried and encapsulated matrices. 2-Methyloxolane provided a higher total carotenoid content (4.75–5546.96 µg/g) compared to the other solvents tested in all the matrices, proving a promising bio-based solvent to replace traditional organic ones for the extraction of microalgal carotenoids.

Aim: Volatile organic compounds (VOCs) are being studied as potential biomarkers in many infections. Therefore, this study aimed to analyze the volatile profile of three Gram-positive bacteria of clinical relevance to identify potential volatile biomarkers that allow their differentiation. Methods and results: L. monocytogenes, S. aureus, and E. faecalis clinical isolates were inoculated in a thioglycollate medium until grown. Then, VOCs were extracted by solid-phase microextraction, and the data obtained were subjected to multivariate analysis. According to our results, there was a high production of aldehydes in E. faecalis. In the case of alcohols, they only increased in L. monocytogenes, while ketones were produced significantly in all three bacteria, mainly due to acetoin. Acids were produced significantly in E. faecalis and L. monocytogenes. Conclusions: Potential biomarkers of L. monocytogenes could be 1-butanol and 2-methylbutanoic acid. In the case of E. faecalis, the VOC most related to its presence was nonanal. Lastly, potential biomarkers of S. aureus could be isoamyl butanoate and methionol, although some pyrazines have also been associated with this bacterium. Significance and impact of the study: The identification of potential biomarkers of these clinically relevant bacteria could open the way for the diagnosis of these infections through the analysis of volatile compounds.

The moisture content of immersion vacuum-cooled sausages with modified casings containing citrus fruit extracts under different storage conditions was studied using hyperspectral imaging (HSI) associated with chemometrics. Different pre-processing combinations were applied to improve the robustness of the model. The partial least squares regression model, employing the full reflectance spectrum with pre-treatment of the standard normal variate, showed calibration coefficients of determination (Rc2) of 0.6160 and a root mean square error of calibration (RMSEC) of 2.8130%. For the first time, prediction maps developed via HSI visualized the distribution of moisture content in the immersion vacuum-cooled sausages with unique modified casings in response to fluctuating storage conditions. The prediction maps showed exact parts with high water content, which will help us to monitor and prevent mold growth. The combination of HSI with multivariate analysis not only quantifies changes in moisture content but also visually represents them in response to various casing treatments under different storage conditions, illustrating the significant potential for real-time inspection and early mold detection in sausages within the processed meat industry.

Carotenoids are ubiquitous and versatile isoprenoid compounds. The intake of foods rich in these pigments is often associated with health benefits, attributable to the provitamin A activity of some of them and different mechanisms. The importance of carotenoids and their derivatives for the production of foods and health-promotion through the diet is beyond doubt. In the new circular economy paradigm, the recovery of carotenoids in the biorefinery process is highly desirable, for which greener processes and solvents are being advocated for, considering the many studies being conducted at the laboratory scale. This review summarizes information on different extraction technologies (ultrasound, microwaves, pulsed electric fields, pressurized liquid extraction, sub- and supercritical fluid extraction, and enzyme-assisted extraction) and green solvents (ethyl lactate, 2-methyltetrahydrofuran, natural deep eutectic solvents, and ionic liquids), which are potential substitutes for more toxic and less environmentally friendly solvents. Additionally, it discusses the results of the latest studies on the sustainable green extraction of carotenoids. The conclusions drawn from the review indicate that while laboratory results are often promising, the scalability to real industrial scenarios poses a significant challenge. Furthermore, incorporating life cycle assessment analyses is crucial for a comprehensive evaluation of the sustainability of innovative extraction processes compared to industry-standard methods.

Introduction: An investigation was conducted using a hyperspectral imaging (HSI) system to non-invasively estimate adenosine triphosphate (ATP) content in vacuum packaged sausages in different modified casing treatments added with orange extracts after a year of storage at 4°C. Methods: Various pre-processing combinations were applied to the spectra to enhance the performance of partial least squares regression (PLSR). Results and discussion: PLSR models, utilising the full absorbance spectrum with pre-treatment of standard normal variate combined with 1st derivative,exhibited prediction coefficients of determination (Rp2) reaching up to 0.6629. A distribution map developed through MATLAB was employed to display the location and concentration of ATP content in these unique sausages for the first time. The integration of HSI and multivariate analysis not only quantifies but also visually represents the changes in ATP content response to the different casing treatments, demonstrating the significant potential for real-time inspection in the processed meat industry.

Propyl-propane thiosulfonate (PTSO), an antioxidant organosulfur compound present in the genus Allium, has become a potential natural additive for food and feed, as well as a possible biopesticide for pest control in plants. A toxicological assessment is necessary to verify its safety for livestock, consumers, and the environment. As part of the risk assessment of PTSO, this study was designed to explore its potential reproductive toxicity in mice following the OECD 416 guideline. The investigation spans two generations to comprehensively evaluate potential reproductive, teratogenic, and hereditary effects. A total of 80 CD1 mice per sex and generation were subjected to PTSO exposure during three phases (premating, gestation, and lactation). This evaluation encompassed three dose levels: 14, 28, and 55 mg PTSO/kg b.w./day, administered through the feed. No clinical changes or mortality attributed to the administration of PTSO were observed in the study. Some changes in the body weight and food consumption were observed, but not related to sex or in a dose-dependent manner. The two parental generations (F0, F1) exhibited normal reproductive performance, and the offspring (F1 and F2) were born without any abnormalities. The serum sexual hormone levels (progesterone -P-, testosterone -T-, estradiol -E2-, follicular stimulating hormone -FSH-, and luteinizing hormone -LH-) were in a normal range. Although significant changes were observed in the sperm analysis in the case of F0 group, no variation was found for F1 group, and no alterations in fertility were recorded either. The absolute organ weights and relative organ weight/body weight and organ weight/brain weight ratios, and the complete histopathological study, showed no significant alterations in males and females for all the generations considered. Considering all the results obtained, PTSO is not considered a reproductive or developmental toxicant in mice under the assayed conditions. These results support the go

Aim: Volatile organic compounds (VOCs) are being studied as potential biomarkers in many infections. Therefore, this study aimed to analyze the volatile profile of three Gram-positive bacteria of clinical relevance to identify potential volatile biomarkers that allow their differentiation. Methods and results: L. monocytogenes, S. aureus, and E. faecalis clinical isolates were inoculated in a thioglycollate medium until grown. Then, VOCs were extracted by solid-phase microextraction, and the data obtained were subjected to multivariate analysis. According to our results, there was a high production of aldehydes in E. faecalis. In the case of alcohols, they only increased in L. monocytogenes, while ketones were produced significantly in all three bacteria, mainly due to acetoin. Acids were produced significantly in E. faecalis and L. monocytogenes. Conclusions: Potential biomarkers of L. monocytogenes could be 1-butanol and 2-methylbutanoic acid. In the case of E. faecalis, the VOC most related to its presence was nonanal. Lastly, potential biomarkers of S. aureus could be isoamyl butanoate and methionol, although some pyrazines have also been associated with this bacterium. Significance and impact of the study: The identification of potential biomarkers of these clinically relevant bacteria could open the way for the diagnosis of these infections through the analysis of volatile compounds.

The employment of cover cropping has been developed in vineyards to mitigate soil erosion and the massive use of herbicides, but the effects on crop yields and berry quality have been little explored. Glycosidic aroma precursors constitute the aroma potential of grapes and have remarkable relevance in neutral grapes, such as Syrah. These compounds tend to be affected by environmental conditions and stressors; therefore, the influence of cover crops on aroma precursors has been studied for the first time. For this purpose, bound aroma compounds from Syrah cv. must obtained from conventional and organic vineyards, subjected to soil tillage and to the influence of different amounts of Zulla cover crop, were extracted and analysed. This experiment was carried out over three consecutive harvests (2019, 2020 and 2021). 40 aglycones were detected, mainly C13-norisoprenoids and terpenes. The last harvest (2021) accounted for the highest amount of precursors, owing to the exceptional amount of isodurene, naphthalene and 2-methylnaphtalene. The year Zulla was planted (2019), treatments with lower Zulla “pressure” increased aroma precursors. In the second vintage (2020), the general impact of Zulla was negative. Decreasing the amount of aglycones with the largest amount of cover crop increased the presence of aglycones in the must. In the last harvest (2021), the two highest levels of Zulla resulted in an increase of the aromatic precursors determined in the must. These results show that the effects of the presence of Zulla are strongly vintage-dependent and probably on the development of the roots. Furthermore, the last vintage results indicate that the employment of Zulla cover crops could be favourable for varieties such as Syrah, a neutral aroma grape, where bound forms are largely responsible for the potential aroma in the resulting wines.

Fortified wines covered by a Protected Designation of Origin (PDO) are high-quality products appreciated by consumers, whose diversity has increased in recent years, leading to an increased vulnerability to fraud. In this work, for the first time, an excitation-emission fluorescence spectroscopy method combined with two chemometric approaches was developed for the characterization and authentication of PDO fortified wines. A visual assessment of fluorescence landscapes pointed out different trends. The excitation-emission matrix (EEM) was decomposed using Parallel Factor Analysis (PARAFAC) for the extraction of potential fluorophores, or unfolded, and then, the resulting matrices were subjected to Principal Component Analysis (PCA) and Partial Least Squares-Discriminant Analysis (PLS-DA). Both approaches were able to discriminate the wine type within each PDO, the PDO within a wine type, and the production process. The proposed analytical and chemometric tools could be used as an alternative control method for a rapid screening of Spanish PDO fortified wines.

Artisanal cheeses are part of the heritage and identity of different countries or regions. In this work, we investigated the spectral variability of a wide range of traditional Brazilian cheeses and compared the performance of different spectrometers to discriminate cheese types and predict compositional parameters. Spectra in the visible (vis) and near infrared (NIR) region were collected, using imaging (vis/NIR-HSI and NIR-HSI) and conventional (NIRS) spectrometers, and it was determined the chemical composition of seven types of cheeses produced in Brazil. Principal component analysis (PCA) showed that spectral variability in the vis/NIR spectrum is related to differences in color (yellowness index) and fat content, while in NIR there is a greater influence of productive steps and fat content. Partial least squares discriminant analysis (PLSDA) models based on spectral information showed greater accuracy than the model based on chemical composition to discriminate types of traditional Brazilian cheeses. Partial least squares (PLS) regression models based on vis/NIR-HSI, NIRS, NIR-HSI data and HSI spectroscopic data fusion (vis/NIR + NIR) demonstrated excellent performance to predict moisture content (RPD > 2.5), good ability to predict fat content (2.0 < RPD < 2.5) and can be used to discriminate between high and low protein values (∼1.5 < RPD < 2.0). The results obtained for imaging and conventional equipment are comparable and sufficiently accurate, so that both can be adapted to predict the chemical composition of the Brazilian traditional cheeses used in this study according to the needs of the industry.

Hydroxytyrosol (HT) is a well-known compound for its bioactive properties. It is naturally present in olives, olive oil, and wine. Its presence in wines is partly due to its production during alcoholic fermentation by yeast through a hydroxylation of tyrosol formed through the Ehrlich pathway. This work aims to explore the influence of yeast assimilable nitrogen (YAN) and glucose content as precursors of HT formation during alcoholic fermentation. Commercial Saccharomyces cerevisiae QA23 and its metabolically engineered strain were used to ferment synthetic must. Each strain was tested at two different YAN concentrations (210 and 300 mg L−1) and two glucose concentrations (100 and 240 g L−1). This work confirms that the less YAN and the more glucose, the higher the HT content, with fermentations carried out with the metabolically engineered strain being the ones with the highest HT content (0.6 mg L−1).

The dataset include the raw data of the analysys of HPLC-MS/MS for tyrosol and hydroxytyrosol. The samples were from fermented synthetic must by the yeas strain Red Fruit in different conditions of YAN (210 mg/L and 300 mg/L) and different glucose conditions (100 g/L y 240 g/L).

Los ácidos grasos trans son más perjudiciales desde el punto de vista nutricional que los ácidos grasos saturados. Una ingesta excesiva de grasa trans afecta principalmente al sistema cardiovascular, aumentando la incidencia de cáncer y otras patologías. En 2004, Dinamarca y Canadá lideraron la limitación de su contenido en alimentos al 2% sobre grasa total. Otra medida adoptada fue la obligatoriedad de incluir información sobre grasa trans en el etiquetado, propuesta por la Food and Drug Administration (FDA) de EE. UU. a partir de 2006. En 2015, La FDA prohibió uso de aceites parcialmente hidrogenados, principal fuente de los ácidos grasos trans de origen industrial. En 2019, la Comisión Europea finalmente restringió el contenido de grasa trans de origen industrial en alimentos del 2%, sobre grasa total. Aún existen regiones en países del Este Europeo, antiguas repúblicas soviéticas, zonas asiáticas (India y Pakistán) y gran parte de África donde se detectan cifras muy altas y preocupantes de grasa trans en alimentos procesados, debido a la falta de regulaciones efectivas. La Organización Mundial de la Salud (OMS) está implementando el programa REPLACE para eliminar el uso de la grasa trans a nivel mundial. En este trabajo se analizaron margarinas españolas reformuladas (“cero trans”) que presentaban niveles de grasa trans inferiores al 0,5%, sobre grasa total. Se empleó el método de análisis de infrarrojos ATR-FTIR (-2D) de segunda derivada, el cual se demostró ser más rápido, eficaz y sencillo que el método de cromatografía de gases. Antes de las reformulaciones, la carga de grasa trans en margarinas era muy alta en países como Canadá, Estados Unidos o Países Bajos. Se evaluaron también varios productos tradicionalmente ricos en grasa trans (dónuts, galletas, snacks, palomitas de maíz, sopas deshidratadas y alimentos de comida rápida), encontrando que los niveles de grasa trans eran inferiores al 1% sobre la grasa total, excepto en los casos de las palomitas de m, From a nutritional point of view, trans-fatty acids are even more harmful than saturated fatty acids. Excessive intake of trans fat primarily affects the cardiovascular system, increasing the incidence of cancer and other pathologies. In 2004, Denmark and Canada led the way in limiting trans-fat content in food to 2% of total fat. Another measure implemented was the mandatory inclusion of trans fat information on labeling, proposed by the U.S. Food and Drug Administration (FDA) starting in 2006. In 2015, the FDA banned the use of partially hydrogenated oils, the main source of industrially produced trans fatty acids. In 2019, the European Commission finally restricted industrial trans-fat content in food to 2% of total fat. There are still regions in Eastern European countries, former Soviet republics, Asian areas (India and Pakistan), and much of Africa where very high and concerning levels of trans fat in processed foods are reported due to ineffective regulations. The World Health Organization (WHO) is implementing the REPLACE program to eliminate trans fat use globally. In this study, reformulated Spanish margarines ("zero trans") were analyzed, showing trans-fat levels below 0.5% of total fat. The second derivative ATR-FTIR (-2D) infrared analysis method was used, proving to be faster, more effective, and simpler than gas chromatography. Prior to the reformulations, the trans-fat content in margarines was very high in countries like Canada, the United States, or the Netherlands. Various products traditionally high in trans-fat (doughnuts, biscuits, snacks, popcorn, dried soups, and fast food) were also evaluated, revealing that trans-fat levels were below 1% of total fat, except for cases like McDonald's popcorn and French fries, which ranged from 1.1% to 2%. In no instance did they exceed the legal limit of 2%. Out of the 23 samples of edible vegetable oils analyzed (olive, sunflower, corn), only 7 provided information on quality and authenticity indices (acid

La calidad del aceite de oliva virgen se puede evaluar de múltiples formas, aunque la única recogida por las reglamentaciones se basa en la evaluación de parámetros sensoriales y fisicoquímicos. Los compuestos volátiles son los responsables del apreciado aroma del aceite de oliva virgen y los compuestos fenólicos del sabor y de las sensaciones del trigémino. La oxidación tiene lugar desde el mismo momento en que el aceite es extraído del fruto y altera cuali- y cuantitativamente el perfil volátil y fenólico del aceite de oliva virgen, haciendo así que éste se degrade y cambie de categoría, lo que produce pérdidas económicas para los productores. El objetivo de esta Tesis Doctoral fue desarrollar estrategias analíticas para la preservación y mejora de la calidad de aceites de oliva virgen extra. Este objetivo se llevó a cabo con la aplicación tanto de técnicas espectroscópicas como cromatográficas (GC-FID, GC-MS y HPLC-DAD) que permitieron la separación y cuantificación de compuestos volátiles y fenólicos. Los resultados muestran la existencia de interacciones entre componentes menores de la matriz alimentaria (fenoles y volátiles), lo que afecta a la liberación de los compuestos volátiles y, por tanto, a la percepción de los mismos. Asimismo, diferentes técnicas de preservación, como la flavorización (adición de plantas) y la congelación, han mostrado ser técnicas adecuadas para mantener la calidad original del aceite de oliva virgen extra. Aunque la oxidación es un proceso ineludible, se ha observado que en las muestras flavorizadas o congeladas la generación de los compuestos de oxidación es más lenta que en las muestras conservadas en las condiciones de almacenamiento de un supermercado. El estudio del efecto de la flavorización en el perfil fenólico de un aceite de oliva virgen extra mostró unos resultados parecidos a los obtenidos con compuestos volátiles, es decir, que la adición de plantas ralentizó el proceso oxidativo sin llegar nunca a detenerlo. Por otro

El dióxido de titanio (TiO2) es un pigmento blanco muy utilizado en la industria debido a que confiere un color blanco excepcional y una elevada opacidad y brillo gracias a que tiene la capacidad tanto de absorber como de dispersar la luz ultravioleta (UV). Se emplea en la industria alimentaria como aditivo (E171) y en la industria farmacéutica y cosmética como excipiente opacificante en la elaboración de medicamentos y como filtro UV en protectores solares. Debido a su gran prevalencia en productos de uso cotidiano, sobre todo en forma de nanopartícula (NP), crea preocupación por su seguridad. En este trabajo se aborda el TiO2 desde el punto de vista de los efectos tóxicos para la salud humana estudiados en diferentes modelos in vitro e in vivo y para ello se ha llevado a cabo una revisión bibliográfica de la literatura científica de las bases de datos PubMed y ScienceDirect. Además, esta revisión resume la normativa actual del TiO2 en Europa. Los resultados obtenidos muestran la existencia de una gran controversia acerca de la toxicidad que las NPs de TiO2 producen en los humanos. Aunque algunos trabajos afirman que las NPs de TiO2 no son nocivas para el ser humano, existe una cantidad considerable de estudios que demuestran sus efectos tóxicos, tanto citotóxicos como genotóxicos, en modelos animales. Aún no existe un consenso entre la comunidad científica, pero de momento en Europa se ha prohibido el uso del TiO2 en los alimentos y se está estudiando la posibilidad de hacer lo mismo con los productos farmacéuticos y cosméticos. Por todo ello, es de gran importancia que se llegue a un acuerdo definitivo sobre la toxicidad de este nanomaterial.

Los alcaloides de la pirrolizidina (AP) son un tipo de alcaloides derivados de la ornitina sintetizados exclusivamente por plantas. Están formados por una base de necina esterificada con ácido nécico y son estructuralmente muy diversos debido a las numerosas combinaciones posibles entre las bases de necina y los diferentes tipos de ácidos nécicos. Estos alcaloides se encuentran ampliamente distribuidos, especialmente en las familias Apiaceae, Apocynaceae, Asteraceae, Boraginaceae, Fabaceae, Lamiaceae, Orchidaceae y Urticaceae. De esta forma, los AP pueden ser ingeridos accidentalmente por los seres humanos a través de productos medicinales derivados de plantas, infusiones de té, suplementos a base de polen, miel contaminada y plantas de cultivo. Los AP no son tóxicos en su forma original, sino que requieren de una bioactivación hepática previa, siendo los metabolitos pirrólicos los responsables de los efectos tóxicos y el hígado, el órgano más afectado. La presente revisión tiene, por tanto, como objetivo, poner de manifiesto en modelos experimentales tanto in vitro como in vivo los efectos tóxicos que se producen tras la exposición a los AP. Para ello, se han seleccionado un total de 27 artículos en relación con la toxicidad de los AP. En ellos se evidencia una clara dependencia de la estructura con el potencial tóxico de cada AP. Además, los resultados observados incluyeron numerosos mecanismos de acción de los AP, siendo los principales la formación de aductos con proteínas, glutatión y ADN y la alteración de la homeostasis de ácidos biliares y del ciclo celular. Por lo tanto, se considera que los AP presentan un alto potencial hepatotóxico y genotóxico y, debido a su presencia en alimentos consumidos ampliamente en todo el mundo, suponen un riesgo potencial para la salud.

La obesidad ha pasado a ser uno de los principales problemas de salud pública en todo el mundo, triplicándose su prevalencia en Europa en las últimas décadas. El mayor problema es su evidencia en ser un factor predisponente para un gran número de enfermedades como las cardiovasculares, las cuales son consideradas según la OMS (Organización Mundial de la Salud) como la principal causa de muerte mundial. La obesidad es una enfermedad multifactorial, relacionada con alteraciones de factores genéticos, de derivados del medio ambiente y de hábitos personales. Además de todos estos factores, se ha comprobado que los contaminantes presentes en los alimentos pueden tener un impacto importante en el desarrollo de la obesidad. La exposición a las sustancias obesógenas es un factor poco estudiado en la pandemia de la obesidad, lo cual es un error, ya que están muy presentes en nuestro entorno. Los contaminantes con efecto obesogénico son compuestos químicos que pueden alterar el metabolismo y la regulación del peso corporal a través de diversos mecanismos. En este trabajo se realizará una revisión de la literatura científica, para examinar algunos contaminantes obesogénicos presentes en alimentos; se llevará a cabo un análisis para determinar la prevalencia de estos contaminantes en diferentes alimentos; se estudiará sus mecanismos de acción y también se realizará una búsqueda exhaustiva de medidas para reducir o controlar los niveles de estos contaminantes en productos alimenticios, con el fin de disminuir su exposición en humanos.

El consumo de drogas de abuso es un fenómeno de gran relevancia en nuestra sociedad y sus consecuencias han ido variando a lo largo de los años al ser la mayoría consumida sin concienciación alguna, aumentando el número de incidencias derivadas de las mismas. Por consiguiente, la legislación actual y el plano judicial de nuestro país ha necesitado ser modificado para ajustarse a una multitud de delitos e incidentes que han ocasionado y siguen ocasionando las drogas lícitas e ilícitas con el paso del tiempo. Esta revisión bibliográfica, se centra en seis sustancias de abuso (etanol, cannabinoides, hipnosedantes, cocaína, GHB y éxtasis) que actualmente presentan gran repercusión y que, en mayor o menor medida, conllevan una fuerte incidencia en el plano delictivo y criminal. Se proporciona información de la prevalencia de dichas sustancias, su mecanismo de acción, los efectos derivados y los delitos asociados a su consumo, así como la pena criminal que acarrearían dichas conductas delictivas. Con toda esta información y haciendo hincapié en la toxicología de estas sustancias y las consecuencias del consumo de estas drogas, se pretende concienciar a la población sobre la gran repercusión de estas sobre las numerosas conductas criminales asociadas.

En la presente Tesis Doctoral, se investigó la toxicidad de diferentes materiales derivados de grafeno, como el óxido de grafeno (OG), el óxido de grafeno reducido (OGr) y sus derivados funcionalizados con dodecil amina (DA) y cloruro de [2-(metacriloiloxi) etil] trimetilamonio (MTAC), para su uso en la industria alimentaria en el área de envasado alimentario. Para garantizar la seguridad de estos materiales en contacto con alimentos, se llevaron a cabo extensos estudios toxicológicos. Como paso previo al estudio de su seguridad se realizó una exhaustiva revisión bibliográfica sobre la toxicidad de los materiales de grafeno en el marco del riesgo alimentario, publicados en la literatura científica hasta la actualidad. Con el fin de determinar las diferentes propiedades fisicoquímicas y así conocer la identidad de cada uno de los derivados de estudio, se llevó a cabo una caracterización fisicoquímica y morfológica de los derivados de grafeno elegidos. Los resultados revelaron diferente contenido atómico y diferente carga, además de la aglomeración de las partículas. La evaluación toxicológica se centró modelos posibles diana de una exposición oral. Se realizaron ensayos in vitro utilizando líneas celulares representativas del sistema digestivo (Caco-2) y el hígado (HepG2). Se observó la internalización de los materiales en estas células, y se detectó citotoxicidad y estrés oxidativo, especialmente a las concentraciones más altas. Se llevó a cabo una digestión gastrointestinal in vitro para simular las condiciones del tracto digestivo y evaluar cómo afectaba a la toxicidad de los materiales. Se encontraron cambios en la morfología de las partículas y en la toxicidad después de la digestión, con disminución de la toxicidad en el caso de OGr pero aumento en los derivados funcionalizados. Para la posible comercialización de estos compuestos y antes de su incorporación a los envases alimentarios, se debe llevar a cabo una evaluación del potencial mutagénico y genotóxico (

Nowadays there is an increasing concern about exposition during prenatal stage to environmental pollutants such as metals, that make pregnant women a vulnerable group of population. Numerous studies have shown associations between the prenatal exposition to some metals and an impact on cognitive, motor and intellectual development of the child. Metals and metalloid are ubiquitous in the environment and pregnant women are exposed to them though their diet, lifestyle factors or occupational and environmental sources. One hundred of maternal and one hundred of cord blood samples were obtained at delivery from pregnant women after signing of the informed consent to determine simultaneously levels of Al, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Se and Zn by ICP-MS. Among these metals, essential ones (Cu, Mn, Se and Zn) can have health beneficial effects at low levels, however, in high concentration are potentially toxic. On the other hand, elements such as Al, As, Cd, Hg, Pb are classified as toxic metals, no matter what its concentration was. The aim of this study was to find the potential relationships between these metals and metalloid levels, newborn's parameters, pregnancy details and the epidemiologic information obtained using a questionnaire data from the participant pregnant women from Seville (Spain). A n = 100 of participants have been enrolled, 15.6 % of the women from Virgen del Rocio Hospital were smokers during pregnancy but only 11.1 % from Virgen de Valme had the habit. Dietary habits of all participants from both hospital were quite similar in average rice, fish and canned food consumption. The characteristics of newborns were also quite similar for both hospitals. A positive correlation between maternal and cord blood was found between all metals except for Cr and Cu. The strongest correlation was found for Hg (r = 0.779, p < 0.005). Positive but weaker correlations between maternal blood and lifestyle habits were also established.

There are numerous publications describing the mineral content of row rice and its impact on human health. However, there are scarce studies about the bioaccessibility and health risk assessment of metallic and metalloid elements from cooked and digested rice. Thus, the aims of the present study were i) to determine the concentration of toxic metals (Al, As, Cd, Pb) and trace and essential elements (Ni, Se, Cr, Cu, Mn and Zn) in cooked and digested rice; ii) to evaluate the adult daily intake and iii) to estimate the non-carcinogenic and carcinogenic human risk related to cooked and digested rice consumption. The bioavailability of the elements studied and their contribution to human health risk was obtained by an in vitro digestion method simulating the human digestion. The results obtained evidenced that Pb had the lowest bioavailability, in contrast with As, which had the highest. Concerning the non-carcinogenic risk test, all values obtained in cooked and digested rice were below the toxic threshold. Furthermore, Pb was the smallest contributor to carcinogenic risk, while Cr-values are the closest to the limit (10⁻⁴). Thus, it could be stated that human metallic exposure through rice consumption is overestimated when metals are measured in row rice.

In recent years, methodologies based on spectral analysis, using ultraviolet–visible (UV-Vis) radiation, have experienced an amazing development and have been widely applied in various fields such as agricultural, food, pharmaceutical, and environmental sciences. This straightforward technique has re-emerged with novel and challenging proposals to solve, in a direct and fast way, a wide variety of problems. These reaches would not have been possible without the essential support of chemometrics. In this sense, under the general background of the development in data and computer science, and other technologies, the emergence of innovative ideas, approaches, and strategies endows UV-Vis spectroscopy with a new vitality as an analytical sensor with the capability of significantly improving both the robustness and accuracy of results. This review presents modern UV-Vis spectral analysis, which is on the rise, associated with comprehensive chemometric methods that have become known in the last six years, especially from the perspective of practicability, including spectral preprocessing, wavelength (variable) selection, data dimension reduction, quantitative calibration, pattern recognition, and multispectral data fusion. Most importantly, it will foresee future trends of UV-Vis spectroscopy as an analytical sensor for a spectralprint (nontargeted) analysis.

The acorn-fed Iberian pig is known worldwide due to the quality of the resulting products commercialized after a natural and free grazing period of fattening in the dehesa agroforestry ecosystem. The quality regulation of the pig breed reserves “acorn” denomination for only those products obtained from animals exclusively fed grazing acorns and other natural resources; however, sometimes, feed supplementation of the pig’s diet is fraudulently employed to reach an earlier slaughtering weight and to increase pig stocking rate, a strategy called postre (meaning “feed supplement”). In this sense, although many studies focused on Iberian pig diet have been published, the field detection of feed use for acorn-fed pig during the last finishing stage foraging in the dehesa, a practice which clashes with the official regulation, has not been explored yet. The present study employs a volatilome analysis (gas chromatography coupled to ion mobility spectrometry) of a non-invasive biological sample (faeces) to discriminate the grazing diet of only natural resources, that acorn-fed Iberian pigs are supposed to have, from those pigs that are also supplemented with feed. The results obtained show the suitability of the methodology used and the usefulness of the information obtained from faeces samples to discriminate and detect the fraudulent use of feed for acorn-fed Iberian pig fattening: a classification success ranging between 86.4% and 100% was obtained for the two chemometric approaches evaluated. These, together with the results of discriminant models, are discussed, in addition to the importance that the methodology optimized implies for the Iberian pig sector and market, which is also introduced. This methodology could be adapted to control organic farming animals or other upstanding livestock production systems which are supposed to be fully dependent on a natural grazing diet.

Metabolites produced by an altered gut microbiota might mediate the effects in the brain. Among metabolites, the fecal volatile organic compounds (VOCs) are considered to be potential biomarkers. In this study, we examined both the VOCs and bacterial taxa in the feces from healthy subjects and Alzheimer’s disease (AD) patients at early and middle stages. Remarkably, 29 fecal VOCs and 13 bacterial genera were differentiated from the healthy subjects and the AD patients. In general, higher amounts of acids and esters were found in in the feces of the AD patients and terpenes, sulfur compounds and aldehydes in the healthy subjects. At the early stage of AD, the most relevant VOCs with a higher abundance were short-chain fatty acids and their producing bacteria, Faecalibacterium and Lachnoclostridium. Coinciding with the development of dementia in the AD patients, parallel rises of heptanoic acid and Peptococcus were observed. At a more advanced stage of AD, the microbiota and volatiles shifted towards a profile in the feces with increases in hexanoic acid, Ruminococcus and Blautia. The most remarkable VOCs that were associated with the healthy subjects were 4-ethyl-phenol and dodecanol, together with their possible producers Clostridium and Coprococcus. Our results revealed a VOCs and microbiota crosstalk in AD development and their profiles in the feces were specific depending on the stage of AD. Additionally, some of the most significant fecal VOCs identified in our study could be used as potential biomarkers for the initiation and progression of AD.

Nowadays there is an increasing concern about exposition during prenatal stage to environmental pollutants such as metals, that make pregnant women a vulnerable group of population. Numerous studies have shown associations between the prenatal exposition to some metals and an impact on cognitive, motor and intellectual development of the child. Metals and metalloid are ubiquitous in the environment and pregnant women are exposed to them though their diet, lifestyle factors or occupational and environmental sources. One hundred of maternal and one hundred of cord blood samples were obtained at delivery from pregnant women after signing of the informed consent to determine simultaneously levels of Al, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Se and Zn by ICP-MS. Among these metals, essential ones (Cu, Mn, Se and Zn) can have health beneficial effects at low levels, however, in high concentration are potentially toxic. On the other hand, elements such as Al, As, Cd, Hg, Pb are classified as toxic metals, no matter what its concentration was. The aim of this study was to find the potential relationships between these metals and metalloid levels, newborn's parameters, pregnancy details and the epidemiologic information obtained using a questionnaire data from the participant pregnant women from Seville (Spain). A n = 100 of participants have been enrolled, 15.6 % of the women from Virgen del Rocio Hospital were smokers during pregnancy but only 11.1 % from Virgen de Valme had the habit. Dietary habits of all participants from both hospital were quite similar in average rice, fish and canned food consumption. The characteristics of newborns were also quite similar for both hospitals. A positive correlation between maternal and cord blood was found between all metals except for Cr and Cu. The strongest correlation was found for Hg (r = 0.779, p < 0.005). Positive but weaker correlations between maternal blood and lifestyle habits were also established.

Anatoxin-a (ATX-a) is a cyanobacterial toxin whose occurrence has been reported worldwide and has attracted increasing scientific interest due to its toxicity. Moreover, in nature, ATX-a usually appears together with other cyanotoxins, such as cylindrospermopsin (CYN), so possible interaction phenomena could happen and should be considered for risk assessment purposes. For this reason, the aim of this work was to explore the potential mutagenicity and genotoxicity of pure ATX-a and an ATX-a/CYN mixture using a battery of in vitro assays, including the bacterial reverse-mutation assay in Salmonella typhimurium (OECD 471) and the micronucleus test (MN) (OECD 487) on L5178Y Tk+/− cells. The results showed that ATX-a was not mutagenic either alone or in combination with CYN under the conditions tested. Nevertheless, genotoxic effects were observed for both ATX-a and its mixture with CYN following the in vitro MN assay. The genotoxicity exhibited by ATX-a was only observed in the absence of S9 mix, whereas in the cyanotoxin mixture the concentration-dependent genotoxicity of ATX-a/CYN in vitro was observed only in the presence of S9. Thus, the toxicity induced by cyanotoxin mixtures may vary from that produced by toxins alone, and consequently more studies are necessary in order to perform more realistic risk assessments.

Propyl-propane-thiosulfonate (PTSO) is an organosulfur compound found inAllium spp. Due to its antioxidant and antimicrobial activities, PTSO has been proposed for applications in the agri-food sector, such as feed additive. However, its use with commercial purposes depends on its toxicity evaluation. The present work aimed to perform a pilot-study of toxicokinetic profile of PTSO combining in silico and in vitro techniques, important steps in the risk assessment process. In silico ecotoxicity studies were also performed considering the importance of the environmental impact of the compound before its commercial use. First, an analytical method has been developed and validated to determine the original compound and its metabolites by ultra-performance liquid chromatography-tandem mass spectrometry. The phase I and II metabolism of PTSO was predicted using Meta-Pred Web Server. For the phase I metabolism, rat (male and female) and human liver microsomes were incubated with PTSO and NADPH regeneration system. Furthermore, in the phase II, microsomes were incubated with PTSO and glutathione or uridine 5′- diphosphoglucuronic acid. The analysis revealed the presence of propylpropane thiosulfinate (PTS) originated by redox reaction in phase I, and two conjugates from the phase II: S-propylmercaptoglutathione (GSSP) and S-propylmercaptocysteine (CSSP). Additionally, considering the environmental fate of PTSO and its metabolites, the ADME parameters and the potential ecotoxicity were also predicted using in silico softwares. The results of the ecotoxicity in silico study evidenced that the metabolism induced the formation of detoxified metabolites from the parent compound, except for dimercaprol and 3-mercaptopropane1,2-diol. Further in vivo assays are needed to confirm this prediction.

Yeasts are feasible and efective bioreactors and, therefore, there is a great interest in their industrial employment for the production of a wide range of molecules. In this study, the production by Saccharomyces cerevisiae of bioactive compounds such as hydroxytyrosol (HT), tyrosol (TYR) and melatonin (MEL) vs. volatile compounds in fermented must was studied. The concentration of the bioactive compounds HT and MEL in fermented must employing diferent yeast strains revealed that the higher the concentrations, the lower the amount of volatile compounds determined. This inverse correlation was especially remarkable with respect to the production of higher alcohols, especially 2-phenylethanol (2-PE) and esters. Furthermore, the employment of a modifed Aro4pᴷ²²⁹ᴸ S. cerevisiae QA23 yeast strain which overproduces HT, gave rise to fermented must also higher in 2-PE and their corresponding esters but with an outstanding less presence of other important esters such as ethyl hexanoate and ethyl octanoate. Both premises could point out that S. cerevisiae might have diferent approaches to handling cell stress/toxicity due to their nitrogen metabolism. One detoxifying pathway could be through the production of higher alcohols and these in turn to esters and the other be more related to synthesizing antioxidant molecules such as MEL and HT.

Shrimp side streams represent an important natural source of astaxanthin. Optimization of the astaxanthin extraction process from shrimp side streams is of great importance for the valorization of crustacean side streams and the development of astaxanthin-related products. The combined and independent effects of two innovative extraction technologies (pulsed electric fields (PEFs) and accelerated solvent extraction (ASE)) alone and/or combined in a sequential step, using two different solvents on astaxanthin extraction from two shrimp species, were evaluated. Astaxanthin content in the extracts of shrimp side streams was determined by both spectrophotometric and HPLC assays, being the determination of the carotenoid profiles performed by HPLC analysis. Compared to a solvent extraction control procedure, the astaxanthin content was increased after ASE and PEF treatments, for both shrimp species, independently of the solvent used. The highest recovery (585.90 µg/g) was obtained for the species A. antennatus, with the solvent DMSO when PEF and ASE were combined, while the increase in antioxidant capacity varied depending on the solvent used. HPLC analysis of the samples revealed the presence of unesterified (all-E) astaxanthin, four unesterified Z isomers of astaxanthin and many unresolved astaxanthin esters. Both technologies are useful tools to recover antioxidant valuable carotenoids such as astaxanthin from shrimp side streams.

Las “Jornadas de divulgación científica: Aportaciones de la Toxicología en la investigación de la seguridad de las sustancias y para la sociedad” se celebraron el 19 de mayo de 2023 en la Facultad de Farmacia de la Universidad de Sevilla, gracias a una Ayuda recibida por el VII Plan Propio de la Universidad de Sevilla (VII PPIT-US) para actividades de divulgación científica. El objetivo fue divulgar entre nuestros alumnos los conocimientos científicos por parte de personal docente e investigador altamente cualificado, y también dar a conocer a la sociedad en general el trabajo de investigación científica de alto nivel que se está realizando en la US. La actividad iba dirigida a los alumnos de las asignaturas de “Toxicología”, “Quimioinformática, Investigación e Historia de la Farmacia”, “Laboratorio de Farmacia” (del Grado en Farmacia, Grado en Óptica y Optometría, y Doble Grado en Farmacia y Óptica y Optometría), y las asignaturas de “Toxicología de las Drogas de Abuso” o “Introducción a las Ciencias Forenses” (Grado en Criminología). Durante las Jornadas, que duraron 5,5 horas, se impartieron un total de 6 comunicaciones orales con diferente temática: el grafeno, las cianotoxinas, los aditivos aliáceos en alimentación humana y animal, los estilbenos en los vinos, o los bioplaguicidas; todas ellas sintetizadas en unos trípticos divulgativos repartidos entre los asistentes para su divulgación en su entorno social. Asimismo, se realizaron 2 ponencias invitadas por parte de expertos en Toxicología Forense y Ambiental, respectivamente. La actividad contó con casi un total de 75 asistentes y los resultados de las encuestas mostraron en general un alto grado de satisfacción con las mismas, mostrando las Jornadas como una enriquecedora actividad de divulgación científica, por la variedad de temas tratados, los nuevos conocimientos adquiridos y el acercamiento a la investigación e interés suscitado entre los asistentes., The " Scientific dissemination conference: Contributions of Toxicology in substance safety research and for society" were held on May 19th, 2023 at the Faculty of Pharmacy of the University of Seville, thanks to a financial support received by the VII Plan Propio of the University of Seville (VII PPIT-US) for scientific dissemination activities. The objective was to disseminate scientific knowledge among our students by highly qualified teaching and scientific personnel, and also to inform society in general of the high-level scientific research work that is being carried out in the University of Seville. The activity was aimed at students of the subjects of "Toxicology", "Chemoinformatics, Research and History of Pharmacy", " Laboratory of Pharmacy" (of the Degree in Pharmacy, Degree in Optics and Optometry, and Double Degree in Pharmacy and Optics and Optometry), and the subjects of "Toxicology of the Drugs of Abuse" or "Introduction to Forensic Sciences" (Degree in Criminology). During the Conference, which lasted 5.5 hours, 6 oral communications were given on graphene, cyanotoxins, alliaceous additives in human and animal feed, stilbenes in wines, or biopesticides. All of them were synthesized in informative triptychs distributed among the attendees for their dissemination in their social environment. Likewise, 2 invited presentations were given by experts in Forensic and Environmental Toxicology, respectively. The activity had 75 attendees and the results of the surveys generally showed a high degree of satisfaction with them, showing the Conference as an enriching outreach activity, due to the variety of topics covered, the new knowledge acquired and the approach to research and interest aroused among attendees.

Due to the importance of the authentication of the botanical and geographical origin of honey, this document is focused on the use of phenols as potential chemical markers in an attempt to distinguish and characterize one of the non-floral honey types, oak (Quercus sp.) honey, from other honeydew honeys produced in other regions. The development and validation of ultra-high-performance liquid chromatography with mass spectrometry detection enables the identification of 23 phenolic compounds in 58 Spanish oak honeydew honey samples. The proposed compounds, above all salicylic acid (mean = 24.31 mg 100 g−1), but also p-coumaric acid, p-hydroxybenzoic acid, syringic acid, naringenin, and galangin could further contribute as a helpful tool in the quality control of this non-floral honey, and therefore distinguish it from European honeydew honey and those from other regions. Furthermore, many positive correlations between phenolic compounds, CIELAB color parameters, and antioxidant activity are established. This research presents a complete phenolic composition and the largest sampling of one of the most appreciated honeydew honey varieties. This is also one of the singular studies that have successfully linked individual phenolic acids and flavonoids with physicochemical parameters within the same unifloral honey.

The growing interest in graphene derivatives is a result of their variety of applications in many fields. Due to their use, the oral route could be a potential way of entrance for the general population. This work assesses the biotransformation of reduced graphene oxide (rGO) after an in vitro digestion procedure (mouth, gastric, intestinal, and colon digestion), and its toxic effects in different cell models (HepG2, Caco-2, and 3D intestinal model). The characterization of rGO digestas evidenced the agglomeration of samples during the in vitro gastrointestinal (g.i.) digestion. Internalization of rGO was only evident in Caco-2 cells exposed to the colonic phase and no cellular defects were observed. Digestas of rGO did not produce remarkable cytotoxicity in any of the experimental models employed at the tested concentrations (up to 200 µg/mL), neither an inflammatory response. Undigested rGO has shown cytotoxic effects in Caco-2 cells, therefore these results suggest that the digestion process could prevent the systemic toxic effects of rGO. However, additional studies are necessary to clarify the interaction of rGO with the g.i. tract and its biocompatibility profile.

Due to climate change and anthropogenic activities, the levels of pollution of aquatic and terrestrial environments have increased in the last decades. In this sense, the rise of cyanobacterial blooms, which release secondary metabolites with toxic properties, and the global use of pesticides for agricultural purposes have a negative impact on ecosystems. Thus, it would be interesting to study the concomitance of both types of toxicants in the same sample, since it is possible that they appear together. The aim of the present work was to state the effects of the interaction between the cyanotoxin cylindrospermopsin and the pesticide chlorpyrifos in differentiated SH-SY5Y neuronal cells to assess how they could affect the nervous system. To this end, cytotoxicity, morphological, and acetylcholinesterase activity studies were performed during 24 and 48 h. The results revealed a concentration-dependent decrease in viability and interaction between both toxicants, together with clear signs of apoptosis and necrosis induction. In this sense, different stages on the differentiation process would lead to differences in the toxicity exerted by the compounds both isolated as in combination, which it is not observed in non-differentiated cells. Additionally, the acetylcholinesterase activity appeared not to be affected, which is a clear difference compared to non-differentiated cells. These results show the importance of studying not only the toxicants themselves, but also in combination, to assess their possible effects in a more realistic scenario.

The incidence and interest of cyanobacteria are increasing nowadays because they are able to produce some toxic secondary metabolites known as cyanotoxins. Among them, the presence of cylindrospermopsin (CYN) is especially relevant, as it seems to cause damage at different levels in the organisms: the nervous system being the one most recently reported. Usually, the effects of the cyanotoxins are studied, but not those exerted by cyanobacterial biomass. The aim of the present study was to assess the cytotoxicity and oxidative stress generation of one cyanobacterial extract of R. raciborskii non-containing CYN (CYN−), and compare its effects with those exerted by a cyanobacterial extract of C. ovalisporum containing CYN (CYN+) in the human neuroblastoma SH-SY5Y cell line. Moreover, the analytical characterization of potential cyanotoxins and their metabolites that are present in both extracts of these cultures was also carried out using Ultrahigh Performance Liquid Chromatography-Mass Spectrometry, in tandem (UHPLC-MS/MS). The results show a reduction of cell viability concentration- and time-dependently after 24 and 48 h of exposure with CYN+ being five times more toxic than CYN−. Furthermore, the reactive oxygen species (ROS) increased with time (0–24 h) and CYN concentration (0–1.11 µg/mL). However, this rise was only obtained after the highest concentrations and times of exposure to CYN−, while this extract also caused a decrease in reduced glutathione (GSH) levels, which might be an indication of the compensation of the oxidative stress response. This study is the first one performed in vitro comparing the effect

Virgin olive oil (OO) can be classified into three different categories: extra virgin, virgin and lampante. The official method for this classification, based on physicochemical analysis and sensory tasting, is considered useful and effective, although it is a costly and time-consuming process. The aim of this study was to assess the potential of some analytical techniques for classifying and predicting different OO categories to support official methods and to provide olive oil companies with a rapid tool to assess product quality. Thus, mid and near infrared spectroscopies (MIR and NIR) have been compared by using different instruments and with head-space gas chromatography coupled to an ion mobility spectrometer (HS-GC-IMS). High classification success rates in validation models were obtained using IR spectrometers (>70% and > 80% in average for ternary and binary classifications, respectively), although HS-GC-IMS showed greater classification potential (>85% and > 90%).

The organosulfur compound propyl-propane thiosulfonate (PTSO), mainly found in Allium cepa, has a promising use in the agrifood industry. To confirm its safety for livestock, consumers, and environment, toxicological assessment is needed. In this regard, endocrine-disrupting chemicals (EDCs) are in the spotlight of research. Therefore, as part of the risk assessment of PTSO, in the present work, an in vivo study was performed in mice exposed to PTSO to investigate its potential reproductive toxicity considering fertility, genetic and endocrine endpoints. Five-weeks-old CD1 mice (80 males, 80 females) were exposed for 11 or 16 weeks (males or females, respectively) to different doses of PTSO (0, 14, 28 and 55 mg PTSO/kg b.w./day; 20 animals per group and sex) through the food pellets. No clinical observations or mortality and no changes in absolute organ weights and relative organ weights/body weight or brain ratios occurred during the study. The estrous cycle did not undergo any significant toxicologically relevant change. Most of the sex hormones displayed normal values. Some alterations in the expression of some genes related to reproduction is only observed in females, but they do not appear to have consequences in the development of sex organs. Docking results showed the impossibility of stable binding to estrogen and androgen receptors. Considering all the results obtained, the safe profile of PTSO can be confirmed for different agrifood applications at the conditions assayed.

Bovine tuberculosis is considered a re-emerging disease caused by different species from the Mycobacterium tuberculosis complex (MTC), important not only for the livestock sector but also for public health due to its zoonotic character. Despite the numerous efforts that have been carried out to improve the performance of the current antemortem diagnostic procedures, nowadays, they still pose several drawbacks, such as moderate to low sensitivity, highlighting the necessity to develop alternative and innovative tools to complement control and surveillance frameworks. Volatilome analysis is considered an innovative approach which has been widely employed in animal science, including animal health field and diagnosis, due to the useful and interesting information provided by volatile metabolites. Therefore, this study assesses the potential of gas chromatography coupled to ion mobility spectrometry (GC-IMS) to discriminate cattle naturally infected (field infections) by MTC from non-infected animals. Volatile organic compounds (VOCs) produced from feces were analyzed, employing the subsequent information through chemometrics. After the evaluation of variable importance for the projection of compounds, the final discriminant models achieved a robust performance in cross-validation, as well as high percentages of correct classification (>90%) and optimal data of sensitivity (91.66%) and specificity (99.99%) in external validation. The tentative identification of some VOCs revealed some coincidences with previous studies, although potential new compounds associated with the discrimination of infected and non-infected subjects were also addressed. These results provide strong evidence that a volatilome analysis of feces through GC-IMS coupled to chemometrics could become a valuable methodology to discriminate the infection by MTC in cattle. IMPORTANCE Bovine tuberculosis is endemic in many countries worldwide and poses important concerns for public health because of their