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198 p., Algunos de los principales metabolitos presentes en las microalgas heterotróficas son los ácidos grasos Omega-3 PUFA. Existen retos importantes en el establecimiento de procesos de producción económicamente viables a partir de las microalgas heterotróficas, incorporando fuentes de carbono alternativas a la glucosa. Se han seleccionado las especies de microalgas heterotróficas capaces de crecer empleando como fuente de carbono ácidos grasos y producir omega 3 y otros compuestos bioactivos. Se ha estudiado el efecto de la sustitución de glucosa por ácidos grasos volátiles sintéticos en el crecimiento de las microalgas y la producción de biomasa, caracterizando los compuestos activos presentes y evaluando la citotoxicidad. Finalmente se ha evaluado la obtención de extractos ricos en compuestos activos de naturaleza lipófila mediante la aplicación de UAE con solventes ¿GRAS¿ como proceso más sostenible y de aplicación en alimentación y nutracéutica.

284 p., Owing to the vast amount of organic contaminants detected in environmental water bodies, there is an increasing demand on detecting those compounds that pose a real risk for the environmental ecosystem. The use of high-resolution chemical analysis to detect unknown compounds in combination with ERA studies and in vivo/in vitro bioassays is an effective way to prioritize potential toxicants. In this sense, we carried out the development and validation of multitarget and suspect screening methods to identify simultaneously different CECs (both, known and unknown) in complex environmental aqueous matrixes. Considering that urban WWTPs have been described as one of the main pathways for CECs into aquatic ecosystems, we assessed the efficiency of different secondary treatments to remove organic micropollutants. The use of an ERA strategy allowed the elucidation and prioritization of toxicologically relevant compounds released into the aquatic system. Moreover, a more holistic approach known as effect-directed analysis (EDA), which combines chemical and biological analyses to unravel cause-effect relationships, was applied to identify toxicity drivers in hospital effluents. In this case two different bioassays were used in EDA to assess different environmental endpoints: (i) the in vitro yeast estrogen bioassay (YES) to measure estrogenic activity and (ii) the in vivo sea urchin embryo test (SET) to evaluate apical effects.

El capítulo 9 está sujeto a confidencialidad por la autora. 289 p., Esta tesis investiga diferentes aspectos de la manipulación de biofluidos complejos, como son el sudor, la sangre y el semen a microescala, para mejorar los enfoques de detección, separación y selección en dispositivos microfluídicos. Esto implica la fabricación de materiales sensores basados en alginato, así como su integración en diferentes plataformas microfluídicas para mejorar la detección de analitos. Además, también se investiga la generación de nuevas herramientas para la separación de plasma a partir de muestras de sangre humana completa mediante tecnología de impresión 3D. Por último, también se contempla el diseño y fabricación de novedosas configuraciones de dispositivos microfluídicos para la selección de espermatozoides viables con fines reproductivos.

224 p., Los dispositivos microfluídicos ideales deben ser pequeños, fáciles de operar, portátiles, autónomos y capaces de integrar todas las funciones analíticas requeridas dentro de un mismo chip. El control de flujo es un aspecto crítico a tener en cuenta al diseñar estos sistemas microfluídicos, sin embargo, a menudo se utilizan componentes convencionales y voluminosos que requieren fuentes de alimentación externas y reducen su portabilidad. En esta tesis se investigó la integración de microbombas poliméricas modulares en cartuchos microfluídicos plásticos para el desarrollo de dispositivos microfluídicos autónomos, dando como resultado el desarrollo de una arquitectura universal altamente versátil y adaptable para una amplia gama de volúmenes y tiempos de actuación. Además, los cartuchos microfluídicos se pueden fabricar fácilmente mediante técnicas de prototipado rápido y un proceso de fabricación capa-a-capa, lo que, en combinación con las bajas presiones generadas por las microbombas poliméricas, permite el desarrollo rápido de operaciones fluídicas complejas para el análisis de muestras. A modo de ejemplo, se demostró la aplicabilidad de estos sistemas autónomos para realizar la calibración de la reacción de Griess en el interior de ionogeles o la separación de plasma a partir de muestras de sangre completa. En conclusión, estas arquitecturas combinadas están destinadas a ser un referente en el diseño de operaciones microfluídicas autónomas y personalizables debido a su versatilidad y facilidad de fabricación.

251 p., El presente trabajo se centra en el desarrollo de biomateriales como alternativa sostenible y multifuncional a los productos convencionalmente aplicados en la conservación pétrea. El diseño persigue una estrategia secuencial de bloques de construcción, y en su última fase, explota diversas estrategias sintéticas tales como líquidos iónicos, aceites esenciales y nanopartículas para alcanzar las funcionalidades deseadas. El proceso sintético se asiste por medio de una metodología multianalítica basada en técnicas espectroscópicas y termo-mecánicas, estudios de hidrorepelencia y biocidas. Así, desde fuentes verdes, se logran dos líneas de materiales híbridos epoxi-sílice con propiedades específicamente adaptadas para presentar funciones consolidantes, hidrofóbicas y biocidas, siendo exitosamente validados en sustratos pétreos como productos protectores. Paralelamente, se diseñan y validan tecnologías de limpieza de pátinas de hierro y cobre en superficies pétreas basadas en hidrogeles de origen natural, cargados con líquidos iónicos, con propiedades de captación de metales y actividad biocida. Todas las estrategias realizadas, incluyendo la selección de los precursores de epoxídicos, disolventes, aditivos, así como las metodologías de monitorización y caracterización, son desarrolladas bajo un criterio sostenible, respetuoso con el material y el medio ambiente, y asegurando un proceso de conservación SMART.

Current sample preparation strategies for nanomaterials (NMs) analysis in soils by means single particle inductively coupled plasma mass spectrometry have significant constrains in terms of accuracy, sample throughput and applicability (i.e., type of NMs and soils). In this work, strengths and weakness of microwave assisted extraction (MAE) for NMs characterization in soils were systematically investigated. To this end, different extractants were tested (ultrapure water; NaOH, NH4OH, sodium citrate and tetrasodium pyrophosphate) and MAE operating conditions were optimized by means of design of experiments. Next, the developed method was applied to different type of metallic(oid) nanoparticles (Se-, Ag-, Pt- and AuNPs) and soils (alkaline, acid, sandy, clayey, SL36, loam ERMCC141; sludge amended ERM483). Results show that Pt- and AuNPs are preserved and quantitatively extracted from soils in 6 min (12 cycles of 30 s each) inside an 800 W oven by using 20 mL of 0.1 M NaOH solution. This methodology is applicable to soils showing a wide range of physicochemical properties except for clay rich samples. If clay soil fraction is significant (>15%), NMs are efficiently retained in the soil thus giving rise to poor recoveries (<10%). Labile NMs such as Se- and AgNPs could not be analyzed by means this approach since extraction conditions favors dissolution. Finally, when compared to current extraction methodologies (e.g., ultrasound, cloud point extraction, etc.), MAE affords better or equivalent accuracies and precision as well as higher sample throughput due to treatment speed and the possibility to work with several samples simultaneously.

Beach handball is a fully developed sporting discipline on all five continents which has attracted the attention of researchers in the last decade, resulting in a proliferation of different studies focusing on players but not on referees. The main objective of this cross-sectional research was to determine the physical demands on elite male beach handball referees in four different competitions: U18 male; U18 female; senior male; and senior female. Twelve elite federated male referees (age: 30.86 ± 8 years; body height: 175.72 ± 4.51 cm; body weight: 80.18 ± 17.99 kg; fat percentage: 20.1 ± 4.41%; national or international experience) belonging to the Technical Committee of the Royal Spanish Handball Federation were recruited for this the study. The physical demands required of referees in official matches were measured by installing a GPS device. The sampling frequency used to record their speed and distance was 15 Hz. A triaxial accelerometer (100 Hz) was used to determine their acceleration. An analysis of variance (ANOVA) between competitions with post hoc comparisons using the Bonferroni adjustment was used to compare among categories. A higher distance covered in zone 1 and speeds of 0 to 6 km-h−1 were recorded. Most accelerations and decelerations occurred in zones 0 and 1 (zone 0: 0 to 1 m·s−2; zone 1: 1 to 2 m·s−2). The lack of differences (p > 0.05) between most analysed variables suggest quite similar physical demands of the four analysed competitions. These results provide relevant information to design optimal training plans oriented to the real physical demands on referees in an official competition.

The present work delves into the feasibility of employing a novel structured sorbent referred to as GFAD (Guefoam Adsorption Device) for the determination of volatile organic compounds (VOCs) in liquid samples. The chosen method has been static headspace sorptive extraction-thermal desorption gas chromatography mass spectrometry (HSSE-TD-GC–MS). The GFAD comprises an aluminum cellular material with a distinct replication structure and a solid guest phase consisting of activated carbon particles dispersed within the cavities of the cellular aluminum. The extensive specific surface area, robustness, and exceptional thermal conductivity of this pioneering material offer distinct advantages over commercially available polydimethylsiloxane-based Twister® devices. Therefore, the trapping efficiency for volatile organic compounds is enhanced, and it is possible to perform the analysis of concentrated samples. According to computational simulations, it has been demonstrated that GFAD has a high heat conductivity. As a result, the desorption efficiency is improved, and minimal temperature gradients are generated throughout the GFAD during the heating process. Besides, the energy consumption is significantly lowered, thus aligning with environmentally conscientious and sustainable analytical practices. The experimental results give a proof of the suitability of the GFAD for determining gaseous compounds in liquid samples through HSSE-TD-GC–MS. For volatile species, the new material provides higher peak areas and lower limits of detection than a commercially available Twister® device. Furthermore, the GFAD is reusable, its adsorbing properties remaining unchanged during, at least, 100 consecutive analyses. In addition, unlike to the Twister®, no intense siloxane peaks are observed in the chromatograms obtained with the GFAD. The feasibility of qualitative and semi-quantitative analysis with the new accessory has been demonstrated with both standards and a cereal bioethanol rea

Microwave induced plasma optical emission spectrometry (MIP-OES) has gained widespread attention in the last few years for trace elemental analysis. Among the new generation of MIPs it is worth to mention the microwave-sustained inductively coupled atmospheric-pressure plasma (MICAP) for which previous works have shown similar detection capabilities to those afforded by ICP-OES. Nevertheless, this instrument has not been applied yet to complex matrix sample analysis. Therefore, the goal of this work is to evaluate MICAP-OES performance (e.g., analytical figures of merit, matrix effects, etc.) for elemental analysis of samples of different nature (e.g., environmental, food and polymers). To this end, both spectral and non-spectral interferences were investigated for 19 elements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, Ga, In, Mg, Mn, Ni, Pb, Sr, Tl, Zn) in the presence of inorganic acid, organic and saline solutions and compared to a 5 % w w−1 HNO3 solution. Unlike previous MIPs, experimental data showed that the optimum nebulizer gas flow rate for a given emission wavelength was mostly independent of matrix characteristics. Regarding matrix effects, this device was highly robust operating both inorganic acid and organic matrices. Interestingly, when operating saline matrices, changes on emission signal by easily ionizable elements were less significant than those early reported by alternative MIP cavities. Moreover, due to MICAP spectrometer design employed allows real-time simultaneous analysis, Rh, Pd, Sc and Y were suitable internal standards to minimize non-spectral interferences. Finally, MICAP-OES can be successfully applied to the elemental analysis of different complex matrix samples (i.e., CRM-DW1 Drinking water; BCR-146 Sewage sludge industrial; BCR-185 Bovine liver; BCR-278R Mussel tissue; NIST-1549 Non-fat milk powder; ERM-EC681k Polyethylene (high level) and BCR-483 Sewage sludge amended soil).

This reply is to a comment on the article available online at https://doi.org/10.1007/s40279-018-0947-8. This reply is to a comment, available online at https://doi.org/10.1007/s40279-024-02003-6, on the above article.

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

Microwave-assisted extraction (MAE) treatments seem to be a promising sample preparation strategy to isolate nanomaterials (NMs) from environmental samples prior to single particle inductively coupled plasma mass (spICP-MS) determination. Nevertheless, because previous studies make use of domestic microwave ovens (DMOs), several shortcomings arise that compromise the analysis such as lack of control of experimental variables, limited operating conditions, and uncontrolled sample heating leading to irreproducibility issues. The goal of this work is to adapt previously developed MAE treatments for soil and air filters with the DMO apparatus to state-of-the-art scientific microwave ovens (SMOs) in order to standardize current analytical protocols for NM characterization. Results show that, by working with an SMO, non-labile metallic NMs (Pt-AuNPs) are quantitively extracted from soil and air filter samples unaltered in 10 min and 6 min, respectively, at 1200 W by using 10 mL of NaOH 0.1 M solution. The use of a SMO system allows improving accuracy (above 10% of the particle recovery), precision (above 5% of the RSD) and sample throughput (above 4-fold) when compared to the DMO ones. According to these findings, MAE seems to be a powerful strategy for routine analysis of non-labile NMs in environmental samples.

La obesidad y el sobrepeso forman parte de las enfermedades más prevalentes y mortales en la actualidad convirtiéndose en un peligro para la salud pública. Tras el aumento de afectados, se han desarrollado infinidad de intervenciones con el objetivo de perder peso. Un claro ejemplo son las dietas cetogénicas o restrictivas con los hidratos de carbono. Se han revisado consecuencias a corto plazo de dicha dieta como: cambios en los parámetros antropométricos, cambios en los parámetros clínicos, reducción del apetito y posibles resultados negativos de su seguimiento. En la actualidad, la evidencia indica buenos resultados a corto plazo. Sin embargo, las consecuencias a largo plazo no están claras, falta mucha investigación.

Antecedentes: la microbiota intestinal, compuesta por más de miles de millones de bacterias, desempeña un papel crucial en la salud humana, participando en funciones inmunológicas, metabólicas y nutricionales. Los alimentos fermentados, ricos en probióticos, pueden modular positivamente esta microbiota, contribuyendo a la prevención y tratamiento de diversas enfermedades. Objetivo: el presente trabajo pretende examinar el impacto del consumo de alimentos vegetales fermentados en la microbiota intestinal, mediante una revisión bibliográfica de ensayos clínicos. Metodología: se realizó una búsqueda exhaustiva en las bases de datos Medline y Cochrane, utilizando los términos alternativos al descriptor ‘‘alimentos de soja’’: Natto, Tempeh, Miso, el término Kimchi, los descriptores Fermented Foods y Gastrointestinal Microbiome, y los términos libres Fermented vegetables y Sauerkraut. Los filtros de búsqueda aplicados fueron: Clinical Trial y Human. Los estudios incluidos seguían los criterios de inclusión: ensayos clínicos, intervenciones con alimentos vegetales fermentados, bebidas o preparados a partir de extractos vegetales fermentados y evaluación de cambios en la microbiota intestinal. Los criterios de exclusión fueron: estudios observacionales, estudios de intervención en animales y/o estudios de intervención cuyo alimento fuese un lácteo (por ejemplo; kéfir), no estuviese fermentado (proteína de soja) y/o cuyo extracto no procediese de ningún alimento vegetal fermentado. Resultados y discusión: se hallaron 47 estudios y fueron seleccionados 11 estudios clínicos que evaluaron diversos alimentos vegetales fermentados como el kimchi, chucrut y bebidas fermentadas de avena, entre otros. La calidad metodológica de los estudios fue evaluada utilizando la escala de Jadad y la mayoría poseía una buena calidad metodológica. Se analizó la diversidad microbiana mediante el análisis del gen 16S DNAr y 16S RNAr. En varios estudios se observó una mejora de la salud intestinal a

Antioxidant/antifungal active films based on bio-polyethylene (BPE) added with Nutrabiol®T90 and Tocobiol®Plus natural extracts rich in tocopherols at different concentrations (1 and 3 wt%) were developed by melt-blending followed by compression-molding. Thermal, barrier, mechanical, optical and functional properties of the developed active films were evaluated. The addition of active extracts did not cause important changes in thermal and barrier properties of active films whereas a significant increase in oxidative stability was found. Release kinetics of active additives migration showed higher tocopherol diffusion coefficient and antioxidant capacity, determined by the DPPH and ABTS methods, for films containing 3 wt% of Nutrabiol®T90. This film also delayed polymer oxidation in 260 min and extended strawberries shelf-life during storage for 7 days compared to neat BPE, showing a significant antifungal effect. The studied biomaterials offer great potential to substitute conventional petrol-derived materials at the industrial scale as active food packaging systems to increase the shelf-life of perishable foodstuff.

Introduction: The presence of heavy metals in the environment has been linked to female infertility. Follicular fluid (FF), which surrounds the developing oocyte in the ovary, can provide valuable insights into the content of a number of elements. However, there is a lack of comprehensive studies that analyze trace elements in FF samples using standardized protocols and methods. The objective of this study was to develop a reliable method utilizing ICP-MS/MS without sample digestion to detect 22 analytes in FF samples. Methods: Four FF samples (n = 4) were obtained from patients undergoing in vitro fertilization (IVF) treatments. These were adequately aliquoted and processed. They were subsequently analyzed via ICP-MS/MS, both in He and no-gas mode. Finally, the data of interest were compiled in a database. Results: Analyte recovery ranged from 70% to 130%, with better results observed in no-gas mode compared to He mode. Among the 22 elements analyzed, only 9Be, 140Ce, 111Cd, 139La, 208Pb, and 238U were not detected. Minor concentrations were observed for 137Ba, 209Bi, 59Co, 55Mn, 95Mo, 60Ni, 121Sb, 118Sn, 205Tl, and 51V, while intermediate concentrations were found for 7Li and 88Sr. Major concentrations were identified for 52Cr, 85Rb, 47Ti, and 66Zn. Conclusions: A new procedure was developed in this study, with several advantages. One of them is the good results in terms of the recovery of a wide variety of elements using ICP-MS/MS in the poorly studied biological matrix that is follicular fluid. Another advantage is the low amount of sample required to perform the analysis and the development of a green method where the sample is not digested and not diluted, which allowed us to avoid the excessive dilution of the concentration of analytes. Moreover, the developed method provides a novel approach to diagnose and predict health risks in women with gynecological pathologies and to assess their overall health, including reproductive health.

Sample preparation plays a pivotal role in chemical analysis, serving to isolate target analytes from diverse matrices and enhance measurement selectivity and sensitivity. This review examines microextraction's eco-friendliness versus tradition, focusing on LPME and EME systems for acidic compounds. Different solid supports (polymeric and gel membranes) implemented in different configurations are evaluated. These innovative techniques reduce the consumption of chemicals and offer enhanced environmental safety. To determine the greenness of these techniques, we employ three widely recognized metrics: Analytical Eco-Scale, Green Analytical Procedure Index (GAPI), and Analytical GREEnness (AGREE). Our comparative analysis provides insights into the strengths and weaknesses of these metrics and offers a holistic perspective on the greenness of microextraction techniques. This review contributes to the ongoing efforts in Green Analytical Chemistry by facilitating the selection of environmentally benign sample preparation methods, thus promoting sustainable laboratory practices, and minimizing adverse environmental impacts.

Searching for technologies to combat emerging pollutants such as dyes and pharmaceuticals is arduous. Plant polysaccharides have been used to synthesize photocatalysts as strategies for green technology. The present study aimed to synthesize TiO2 nanostructure photocatalytic using cashew tree gum. Structural, morphological, and optical characterization was carried out to verify the gum's effect on the growth of nanostructures. Photocatalytic tests were performed with Methylene dye (MB) and Ibuprofen (IBP) pollutants under UV irradiation. Structural characterization demonstrated the formation of anatase-type TiO2, with a band gap at 3.15 eV. Photocatalytic assays using CGT showed that the material was more efficient in removing MB (43.17 %) when compared to IBP (29.86 %). In addition, scavenger studies indicated that electrons are the species involved in dye degradation. Therefore, the results are promising for using TiO2 nanoparticles obtained with gum to remove pollutants.

Background: In recent decades, green chemistry has been focusing on the adaptation of different chemical methods towards environmental friendliness. Sample preparation procedures, which constitute a fundamental step in analytical methodology, have also been modified and implemented in this direction. In particular, electromembrane extraction (EME) procedures, which have traditionally used plastic supports, have been optimized towards greener approaches through the emergence of alternative materials. In this regard, biopolymer-based membranes (such as agarose or chitosan) have become versatile and very promising substitutes to perform these processes. Results: Different green metric tools (Analytical Eco-Scale, ComplexGAPI and AGREEprep have been applied to study the evolution of solid supports used in EME from nanostructured tissues and polymer inclusion membranes to agar films and chitosan flat membranes. The main goal is to evaluate the usage of these new biomaterials in the analytical procedure to quantify their environmental impact in the frame of Green Analytical Chemistry (GAC). In addition, both RGB model and BAGI metrics have been employed to study the sustainability of the whole procedure, including not only greenness, but also analytical performance and feasibility aspects. Results obtained after the performance of the mentioned metrics have demonstrated that the most efficient and environmentally friendly analytical methods are based on the use of chitosan supports. This improvement is mainly due to the chemical nature of this biopolymer as well as to the removal of organic solvents. Significance: This work highlights the advantages of biodegradable materials employment in EME procedures to achieve green analytical methodologies. These materials also contribute to raise the figure of merits regarding to the quantification parameters in a wide range of applications compared to classical supports employed in EME, thus enhancing sustainability of procedures.

Quality control of flour is essential to control the quality of bread produced from it. We propose a control method based on the morphological characteristics of the granules of starch. The automation of the identification, segmentation and determination of the average size of the granules of starch of each of the cereals that make up a flour, from microscopy images, is an essential procedure for producers who want to produce bread under the protected geographical indication (PGI) ‘Galician Bread’. This identification and counting procedure, if performed manually, is a tedious activity for a trained expert, and is very time consuming. Thus, automating this task would streamline the process, in addition to saving a great deal of time. This paper addresses this problem by using deep learning approaches (Mask R–CNN) to predict the type of the granule of starch and its size for the first time. The trained models are then evaluated with the same raw microscopy images of these granules observed under polarized light, as has been previouly used for manual identification and counting. A dataset comprising 1308 2564 × 1924-pixel images is analysed. The images contain 17000 labelled granules of starch for two types of wheat: commercial wheat flour from ‘Castilla’ (type 0) and the Galician autochthonous flour ‘Caaveiro’ (type 1). The number of samples is approximately the same for each class. Instance segmentation with Mask R–CNN (Model II) achieved valid results for unseen images, with a categorical global accuracy of about 88.6% and with a discrepancy with respect to the areas of the granules as estimated by a human expert of less than 4%. The performance achieved by Mask R–CNN produces a strong correlation between the results of an expert and the results of the network, confirming the practical validity of our proposal

The current study aimed to investigate major knowledge gaps regarding the application of the anodic oxidation (AO) process with boron-doped diamond (BDD) anodes for the remediation of water matrices contaminated with per- and polyfluoroalkyl substances (PFAS). This included: (i) the degradation of ultrashort-chain (C1-C3) and long-chain (C9-C13) PFAS in addition to short- and medium-chain (C4-C8) PFAS, (ii) the application of multi-solute systems with different PFAS content (0.2 µg L−1 versus 2.0 µg L−1) and diversity (24 C1-C13 versus 8 C1-C8) in addition to single-solute systems, (iii) the use of real water matrices in addition to pure water, and (iv) the application of current densities (j) up to 250 mA cm−2 in addition to usual j (≤20 mA cm−2). C1-C4 PFAS with a sulfonated headgroup were the most recalcitrant compounds. By contrast, PFAS ≥ C9 with a sulfonated headgroup and PFAS ≥ C12 with a carboxylic headgroup were potentially instantaneously degraded. The content and diversity of PFAS mainly affected the degradation kinetics of PFEtS (C2), PFPrA (C3), and PFBA (C4). Four real water matrices were under focus: drinking water (DW), urban wastewater after secondary treatment (UWW), and nanofiltration concentrate (NF) and reverse osmosis concentrate (RO) from urban wastewater polishing step. PFAS degradation typically benefited from using real matrices primarily due to the presence of chloride ions and consequent electrogeneration of active chlorine species. However, for waters with a high organic content, namely a chemical oxygen demand (COD) of 319 mg O2 L−1, PFAS degradation was hindered. Furthermore, the removal of most PFAS benefited from the application of j > 20 mA cm−2, and some specific PFAS required the use of j ≥ 250 mA cm−2 to have maximized removal rates.

Ultrasound-accelerated hydrolysis is effectively used for the first time in the release of 3-monochloropropane-1,2-diol (3-MCPD) from its fatty esters. Indirect determination of 3-MCPDE fatty acid esters was performed under alkaline and acid conditions using sodium methoxide and sulfuric acid, respectively, prior to GC-MS analysis. Dispersive liquid-liquid microextraction (DLLME) was used to derivatize the free 3-MCPD with n-heptafluorobutyrylimidazole (HFBI). Two asymmetrical screening designs were used to evaluate parameters affecting the methods’ performances: time, temperature, hydrolytic agent volume, and concentration. A comparative study between both methods was performed. Research showed that comparable results are achieved in terms of linearity (r2 > 0.9995), specificity, accuracy, and precision. Determination limits were lower for the alkaline method (67 ng g−1). Twenty samples of four types of edible oil were assessed using both methods: extra virgin olive oil (EVO), refined sunflower oil, refined olive oil, and palm oil. Results obtained here were comparable and similar to those reported in the literature. Alkaline hydrolysis was the recommended approach and should be used in occurrence studies.

A rapid sample preparation fabric phase sorptive extraction (FPSE) methodology followed by gas chromatography coupled to tandem mass spectrometry is proposed for the first time to determine 12 synthetic musks including nitro-, polycyclic and macrocyclic musk in environmental water and wastewater. An asymmetric screening design of experiments was used to evaluate the influence of nine parameters affecting FPSE in only 16 experiments. The factors included the sol–gel sorbent coating, stirring mode (both extraction and desorption), extraction and desorption time, salting-out effect, sample volume, type of solvent, and desorption solvent volume. The selected conditions imply the use of the sol–gel PDMS sorbent coating, 15 min extraction by ultrasound energy employing 10 mL of sample and 0.5 mL of ethanol as desorption solvent during 5 min. Accuracy and precision were assessed in different real water samples. Matrix effects were evaluated performing recovery studies in several aqueous matrices: river, sea, spring, laundry washing place, and wastewater at different concentration levels (0.1, 2, 10 µg L−1) demonstrating method accuracy (results ranged between 82 and 110%) and good precision (relative standard deviation, RSD < 12% in all cases). Limits of detection (LODs) were below 8 ng L−1 for the analyzed synthetic musks. As extraction was quantitative (exhaustive extraction), calibration was carried out using solvent standards without the need of repeating the extraction step, which is required in most microextraction methods, improving sample throughput, and reducing costs. Finally, the analysis of real contaminated samples revealed the presence of 11 out of the 12 target synthetic musks at concentrations up to 30 µg L−1, three of them banned in cosmetic regulation (musk tibetene, ambrette, and moskene). The developed FPSE based methodology uses low volume (0.5 mL) of a Generally Recognized as Safe (GRAS) solvent (ethanol), as well as minimum energy and time consumptio

Chitosan films enriched with aqueous extract of Sugar kelp Saccharina latissima (SLE) were developed and characterized by measuring the equilibrium moisture, moisture content, water vapor permeability, mechanical properties, antioxidant properties, optical properties, surface morphology and thermostability. The developed films were tested as separators with antioxidant properties for sliced Havarti cheese. The addition of SLE showed a decrease in mechanical properties such as tensile strength from 48.99 to 36.16 MPa and Young's Modulus from 929.49 to 743.71 MPa compared with pure chitosan films. The resulting chitosan-SLE films showed a high free-radical scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+). Moreover, the presence of SLE in the chitosan matrix significantly improved the UV-barrier of the samples. When the chitosan-SLE films were employed as separators for cheese, a significant reduction of 52.8% in cheese lipid oxidation was observed after 45 days of refrigerated storage compared to the control group using chitosan films. Hence, an environmentally sustainable alternative to synthetic and non-biodegradable slice separators has been successfully developed using chitosan, a by-product of the fishing industry, fortified with an extract from sugar kelp, a commonly found brown algae.

Nowadays, frontiers among different sciences are revealed as diffuse, and as a consequence, research must necessarily be faced from an interdisciplinary approach. Similarly, teaching certain topics in Chemistry requires the consideration of developments in other sciences (Mathematics, Biology, Physics, etc.). For instance, the estimation of the parameters of calibration lines in Analytical Chemistry (via linear regression) exemplifies this mandatory interaction since the comprehension of the regression tools should also consider how estimation is regarded from a statistical perspective. This work focuses on how to overcome the contradictions that undergraduate Chemistry students may encounter between the chemists’ and statisticians’ perspectives, when they are lectured on least-squares linear regression. A mixed analytical chemistry−statistics approach is proposed to present a method to get over the discordant issues between both scientific viewpoints.

Ignimbrite rock is a volcanic material located in the Arequipa region (Peru), and for centuries, it has been used as a construction material, giving a characteristic light pastel, white to pink color to the city of Arequipa, with white being the most common. In the present study, the potential use of three types of Arequipa raw materials (ignimbrite rock powder, calcined clay powder, and demolition mortar powder) as the main source of new binders or the manufacture of environmentally friendly mortars, without the addition of ordinary Portland cement (OPC) is discussed. In this work, an in-depth characterization of the materials used was carried out. The proposed fabrication route for geopolymeric materials was considered for the manufacture of binders and mortars using an alkaline solution of NaOH with values between 12 and 18 molar, as a trigger for the geopolymerization process. Geopolymeric mortars were obtained by adding a controlled amount of fine sand to the previously prepared mixture of binder raw material and an alkaline solution. Conventional OPC and geopolymeric mortars manufactured under the same conditions were mechanically evaluated by uniaxial compression tests at a constant compression rate of 0.05 mm/min and under normal conditions of temperature and atmosphere, where the most optimal values were obtained for 15 molar alkaline solutions of ignimbrite without the addition of aggregates, with values of compressive strength of 42 MPa and a modulus elastic of 30 GPa. The results revealed a significant increase in the maximum strength and modulus of elasticity values when the volumetric fractions of OPC are completely replaced with geopolymeric binders in the study conditions of this work, demonstrating the enormous potential of the ignimbrite rock and construction waste studied, as raw material of alternative mortar binders without the addition of OPC. With this work, the ignimbrite rock, of great value in the region and also found in other areas of the

Synthetic micas are materials with interesting properties that combine high charge (high cation exchange capacity) with swelling capacity. Among the various methods for synthesizing this clay, the “NaCl-melt method” is the most widely used, producing a material with excellent crystallinity. Furthermore, synthetic micas are also susceptible to modifications with a wide range of compounds, mainly organic compounds, which further increases their reactivity. Thus, this Review addresses the properties and syntheses of this clay. The types of modifications used and the changes that occur in the properties of this clay are reported, in addition to applications in the removal of contaminating compounds that can be found in water. Research to date has demonstrated that synthetic mica-based adsorbents are versatile in the adsorption of various contaminants, such as metals, pharmaceuticals and others. Therefore, this material can be promising in the adsorption and release of drugs, bioactive compounds, enzymes, proteins, etc., thus increasing its field of application.

A lot of works have shown Curcumin (Cur) as a potential candidate in the treatment of neurodegenerative diseases (NDDs) such as atherosclerosis, stroke, Huntington’s, Alzheimer’s, and Parkinson’s. The therapeutic potential of Cur in NDDs has been linked to its antioxidant, anti-inflammatory, and anti-protein aggregation effects. However, one of the main factors that have limited the application of Cur is the scarcity of clinical trials to evaluate its therapeutic efficacy due to its extremely low aqueous solubility, instability, low oral bioavailability associated with the low aqueous solubility, rapid metabolism, and elimination from the bloodstream. Hydrogel matrixes are an interesting way for Cur carrying, mainly to protect the Cur against instability and enhance the low bioavailability. The encapsulation of Cur in polymeric micelles and hydrogels is an example of an important strategy to facilitate its delivery and release in the human body to protect against several diseases, including in NDDs. Therefore, 3D matrices of hydrogels, made up of polymers, are materials with characteristics and requirements suitable for applications such as drug delivery systems (DDS). This chapter centers around the neuroprotective properties of Cur and its utilization in both the treatment and prevention of NDDs. Almost 180 references are cited ca. 120 of them published in the last 5 years.

375 p., This PhD Thesis is focused on the geochemical study of the Moon and Mars in order to provide science support for current and future space missions. Throughout this thesis a bibliographic review of all the past and current Martian landing missions, as well as their scientific payload was performed. In this work an improved calibration model for the estimation of the forsterite and fayalite content in olivines was proposed. Likewise, the primary, secondary and weathering mineral phases of the LAR 12095 and RBT 04262 Martian meteorites were identified. Though this identification it was posible to trace the history of the primary minerals of Mars and how they are transformed into secondary minerals through different weathering processes. The formation of sulfates already found on Marsand others expected to be found was simulated by laboratory simulation. It was also observed how the Raman response of the previous sulfates synthesized changes as function of temperature. Subsequently, the organic protective capacity of crust soils, smectites and microbioalites was studied. Finally, it has been evaluated how oxidized lunar regolith could serve as a resource for future plant cultivation.

307 p., La degradación del pigmento rojo HgS es un problema de conservación que afecta tanto a la forma mineral, denominada cinabrio, como a los pigmentos sintéticos, conocidos como bermellón. El ennegrecimiento se aprecia tanto en pintura sobre tabla o lienzo conservada museos, con condiciones de humedad relativa y temperatura controladas, como en pintura mural conservada in-situ.En concreto, esta Tesis Doctoral se centra en el estudio de su deterioro en las pinturas murales del Parque Arqueológico de Pompeya, sepultado por la erupción del Vesubio en el año 79 d.C. Las características intrínsecas propias de este yacimiento provocan que, a las amenazas y riesgos habituales para la conservación de otras obras con cinabrio, se sumen fuentes de degradación adicionales.Para evaluar las amenazas para la conservación de las pinturas murales en general, y del cinabrio rojo en particular, en el marco del Parque Arqueológico de Pompeya, la presente Tesis Doctoral se ha dividido en dos partes. La primera se centra en la caracterización exhaustiva de los materiales piroclásticos que destruyeron la ciudad en el 79 d.C. y en la evaluación del impacto de su carga de haluros en el estado de conservación. El desarrollo de metodologías de análisis cuantitativo in-situ para Cl y F en pinturas al fresco facilitará la detección de zonas en riesgo. La segunda parte ha permitido conocer más a fondo la naturaleza mineral del cinabrio de Pompeya, así como estudiar su degradación in-situ y en el laboratorio y comprender mejor su transformación mediante envejecimientos acelerados.

292 p., Como consecuencia de los cambios climáticos ocurridos durante las últimas décadas se prevé una intensificación de las temperaturas y de los periodos de sequía en muchas regiones vitivinícolas, donde Vitis vinífera esta sufriendo desajustes en sus ciclos reproductivo y vegetativo, así como en su fisiológica y metabolismo llegando a un debilitamiento del rendimiento y la calidad de los frutos producidos. Por este motivo, la zona vitivinícola de La Rioja requiere el emplear de nuevas técnicas agrícolas más respetuosas con el medio ambiente que mejoren la tolerancia de las plantas a estas condiciones adversas. En este contexto, el uso de bioestimulantes para minimizar los impactos del estrés hídrico puede ser una técnica prometedora, pero su mecanismo de acción es todavía desconocido en muchos casos.En esta tesis se estudió el mecanismo de acción de determinados bioestimulantes mediante el estudio de cambios morfo-fisiológicos, bioquímicos, y de producción que inducen en una plantación de Vitis vinífera (var. Tempranillo) poco productiva debido al escenario del cambio climático ubicada en La Rioja, y se comparó con un estudio llevado a cabo en la planta modelo Arabidopsis thaliana cultivada bajo déficit hídrico en condiciones controladas.En Vitis vinifera se desarrolló un plan de campo experimental definido por la aplicación foliar de tres productos bioestimulantes comerciales, basados en extractos de algas marinas y aminoácidos vegetales para determinar su mecanismo de acción a través de su perfil fisiológico y bioquímico. Se cuantificaron metabolitos como carbohidratos, ácidos orgánicos y aminoácidos en diferentes tejidos vegetales a través de cromatografía liquida de alto rendimiento (HPLC) acoplada a diferentes detectores para obtener la mayor sensibilidad y la menor incertidumbre en la medida.Igualmente, en Arabidopsis tratadas con los mismo bioestimulantes se llevó a cabo un fenotipado de alto rendimiento de rasgos múltiples (MTHTSM) y estudio metabólico para eval

This review describes a wide variety of analytical approaches for the assessment of human exposure to organic chemicals associated with plastic additives, focusing on works published in the last decade on plasticizers, bisphenols, flame retardants and antioxidants. Physiologically based extraction tests serve as preliminary in-vitro assays to determine the bioaccessibility of these compounds from micro/nanoplastics in body fluids of the gastrointestinal tract, skin, or lung. Whenever plastic-laden compounds become bioavailable, human metabolism is to be monitored through the assessment of phase I and II metabolites. In this regard, analytical methods based on chromatography and mass spectrometry for human biomonitoring of parent compounds and their metabolites in biological samples (mostly urine and plasma) are discussed in depth. This review also covers the role of wastewater-based epidemiology in determining the overall human exposure of a given population to plastic-related species.

Tris (1-chloro-2-propyl) phosphate (TCIPP) is one of the major organophosphate flame retardants present in the indoor and outdoor environment. Knowledge of biotransformation pathways is important to elucidate potential bioavailability and toxicity of TCIPP and to identify relevant biomarkers. This study aimed to identify TCIPP metabolites through in vitro human metabolism assays and finally to confirm these findings in urine samples from an occupationally exposed population to propose new biomarkers to accurately monitor exposure to TCIPP. TCIPP was incubated with human liver microsomes and human liver cytosol to identify Phase I and Phase II metabolites, by liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). Using a suspect-screening approach, the established biomarkers bis (1-chloro-2-propyl) hydrogen phosphate (BCIPP) and 1-hydroxy-2-propyl bis (1-chloro-2-propyl) phosphate (BCIPHIPP) were identified. In addition, carboxyethyl bis (1-chloro-2-propyl) phosphate (TCIPP-M1), bis (1-chloropropan-2-yl) (-oxopropan-2-yl) phosphate (TCIPP-M2) and 1-chloro-3-hydroxypropan-2-yl bis (1-chloropropan-2-yl) phosphate (TCIPP-M3) were identified. TCIPP-M2, an intermediate product, was not reported before in literature. In urine samples, apart from BCIPP and BCIPHIPP, TCIPP-M1 and TCIPP-M3 were identified for the first time. Interestingly, BCIPP showed the lowest detection frequency, likely due to the poor sensitivity for this compound. Therefore, TCIPP-M1 and TCIPP-M3 could serve as potential additional biomarkers to more efficiently monitor TCIPP exposure in humans.

Agricultural management influences the soil ecosystem by affecting its physicochemical properties, residues of pesticides and microbiome. As vineyards grow crops with the highest incidence of pesticides, the aim of this study was to evaluate the impact of conventional and sustainable management systems of vineyards from DOP Ribeiro on the soil’s condition. Samples from soils under three different management systems were collected, and the main soil physicochemical properties were evaluated. A selection of 50 pesticides were investigated by liquid chromatography with tandem mass spectrometry. The bacterial and fungal microbiomes were characterized through amplicon sequencing. The results show that organic agriculture positively influences soil pH and the concentration of some nutrients compared to conventional management. Our microbiome analysis demonstrated that transitioning from conventional to organic management significantly improves several BeCrop® indexes related to key microbial metabolism and soil bio-sustainability. Such a transition does not affect soil alpha diversity, but leads to a higher interconnected microbial network structure. Moreover, differential core genera and species for each management system are observed. In addition, the correlation of the microbiome with geographical distance is evidence of the existence of different microbial terroirs within DOP Ribeiro. Indeed, sustainable management leads to higher nutrient availability and enhances soil health in the short term, while lowering pesticide usage

The incorporation of fibre into pea protein matrices influences their microstructure, yet our understanding of their gut fermentability remains unexplored. In this study, dietary fibres and protein from yellow pea were investigated for their physico-chemical properties and impact on in vitro colonic fermentation using human inoculum. Pea fibre and pea protein blends were studied at different pH and after thermal treatment at 95 °C for 30 min with oscillatory rheology, static light scattering and confocal laser scanning microscopy. The effect on in vitro colonic fermentation was evaluated measuring gas production, ammonia, and short chain fatty acid (SCFA) production. Rheology indicated that during thermal treatment a firmer gel is formed close to the protein isoelectric point with a structure characterised by aggregation, but less particle swelling compared to other pH. Addition of fibre led to higher storage modulus (G′), with the fibre dominating the rheological properties. Fermentation of samples containing protein led to higher levels of ammonia and SCFA compared to only fibres. Blends produced higher amounts of valerate, i-valerate and caproate, and lower amounts of ammonia. Reduced fermentation of proteins in the presence of fibres was also reflected in a more intact microstructure of the protein particles in the digesta. Although thermal treatment of blends caused particle swelling and induced gelation, only small differences could be discerned in the in vitro colonic fermentation outcomes. Our results highlight that potentially harmful fermentation products from protein, such as ammonia, were reduced in the presence of pea hull fibre

The refinement and optimization of a method combining headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry (GC-MS) was successfully performed for the first time to determine seven carbonyl and dicarbonyl compounds, including glyoxal, methylglyoxal, dimethylglyoxal, and malondialdehyde in infant formulae, related to lipid peroxidation. HS-SPME was utilized for simultaneous extraction and derivatization with pentafluorophenylhydrazine (PFPH). Critical parameters such as temperature, pH, extractive phase, and salting-out were meticulously investigated and fine-tuned by an asymmetrical 2232//9 screening design to ensure the method's efficacy and reliability. Optimal conditions included a PFPH concentration of 5 g/L, pH 5.0, head-space extraction at 60 °C within 10 min, utilizing a DVB/CAR/PDMS coating, and a 20% w/w salting-out. The analytical validation of this method, compliant with FDA guidelines, demonstrated exceptional linearity, sensitivity, specificity, precision (RSD ≤13.8%), and accuracy (84.8% ≤ recovery ≤111.5%). The metric approach AGREEprep confirms its eco-friendliness, marking a significant step towards an environmentally conscious approach in infant formula analysis. An occurrence study conducted on 25 infant formula samples revealed widespread carbonyl and dicarbonyl compounds in both powdered and liquid variants. ANOVA results exhibited variations in compound concentrations among different sample groups. Clustering analyses delineated distinct groups based on carbonyl content, indicating the potential of these compounds as markers for lipid peroxidation and food quality assessment. This method serves as a valuable tool for evaluating infant formula quality, stability towards oxidation, and safety.

Suspect and non-target screening (SNTS) methods are being promoted in order to decode the human exposome since a wide chemical space can be analysed in a diversity of human biofluids. However, SNTS approaches in the exposomics field are infra-studied in comparison to environmental or food monitoring studies. In this work, a comprehensive suspect screening workflow was developed to annotate exposome-related xenobiotics and phase II metabolites in diverse human biofluids. Precisely, human urine, breast milk, saliva and ovarian follicular fluid were employed as samples and analysed by means of ultra-high performance liquid chromatography coupled with high resolution tandem mass spectrometry (UHPLC-HRMS/MS). To automate the workflow, the “peak rating” parameter implemented in Compound Discoverer 3.3.2 was optimized to avoid time-consuming manual revision of chromatographic peaks. In addition, the presence of endogenous molecules that might interfere with the annotation of xenobiotics was carefully studied as the employment of inclusion and exclusion suspect lists. To evaluate the workflow, limits of identification (LOIs) and type I and II errors (i.e., false positives and negatives, respectively) were calculated in both standard solutions and spiked biofluids using 161 xenobiotics and 22 metabolites. For 80.3 % of the suspects, LOIs below 15 ng/mL were achieved. In terms of type I errors, only two cases were identified in standards and spiked samples. Regarding type II errors, the 7.7 % errors accounted in standards increased to 17.4 % in real samples. Lastly, the use of an inclusion list for endogens was favoured since it avoided 18.7 % of potential type I errors, while the exclusion list caused 7.2 % of type II errors despite making the annotation workflow less time-consuming.

Introduction: Benzophenones (BPs) are used in various branches of industry as ultraviolet radiation filters, but they pollute the natural environment, penetrate living organisms, and disrupt endocrine balance. Knowledge of the exposure of domestic animals to these substances is extremely scant. The aim of the study was to investigate long-term exposure of companion dogs to BPs and relate this to environmental factors. Material and Methods: Hair samples taken from 50 dogs and 50 bitches from under 2 to over 10 years old were analysed for BP content with liquid chromatography–tandem mass spectrometry. Results: The results revealed that dogs are most often exposed to 2-hydroxy-4-methoxybenzophenone (BP-3) and 4-dihydroxybenzophenone (BP-1). Concentration levels of BP-3 above the method quantification limit (MQL) were noted in 100% of the samples and fluctuated from 4.75 ng/g to 1,765 ng/g. In turn, concentration levels of BP-1 above the MQL were noted in 37% of the samples and ranged from <0.50 ng/g to 666 ng/g. Various factors (such as the use of hygiene and care products and the dog’s diet) were found to affect BP concentration levels. Higher levels of BP-3 were observed in castrated/spayed animals and in animals that required veterinary intervention more often. Conclusion: The results obtained show that the analysis of hair samples may be a useful matrix for biomonitoring BPs in dogs, and that these substances may be toxic to them.

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.