https://hdl.handle.net/10481/18082 2026-04-25T08:25:49Z https://hdl.handle.net/10481/112856 The Role of Analytical Chemistry in Investigating Mycotoxins within the Exposomics Framework Hernández Mesa, Maykel; Narváez, Alfonso; Delgado-Povedano, María del Mar; Gámiz Gracia, Laura; García Campaña, Ana María Mycotoxins are toxic secondary metabolites produced by fungi that frequently contaminate food and constitute a major source of human and animal exposure worldwide. Within the exposome framework, they are increasingly recognized as important chemical stressors due to their widespread occurrence and potential adverse health effects. Analytical chemistry plays a key role in characterizing both external exposure sources and internal exposure burdens. Recent advances, particularly liquid chromatography coupled to tandem mass spectrometry and high-resolution mass spectrometry, have significantly improved sensitivity, accuracy, and the ability to simultaneously detect multiple mycotoxins. This review summarizes the current state of the art and challenges in multi-mycotoxin analysis, including sample preparation and data acquisition strategies for assessing co-exposure in food matrices. It also highlights applications in human biomonitoring, emphasizing the identification of biomarkers in biofluids. Finally, the review discusses the development of comprehensive “mega-methods” to support exposome-based studies and strengthen food safety and public health assessments. Grupo FQM302 - Departamento de Química Analítica. This work was supported by project PID2024-162715OB-I00, funded by MICIU /AEI /10.13039/501100011033 / FEDER, UE; project CNS2024-154893, funded by MICIU/AEI/10.13039/501100011033; and project P24.01227, funded by the ‘Consejería de Universidad, Investigación e Innovación, Junta de Andalucía’. M.H.-M. gratefully acknowledges the grant RYC2023-044255-I, funded by MCIU/AEI/10.13039/501100011033 and FSE+. https://hdl.handle.net/10481/112031 Development and application of p-NIPAM Barriers and Repositories for Microfluidic Flow Control. A Proof of Concept Torres-Molina, María Angustias; Ramos Lorente, Celia Esperanza; Orbe Payá, Ignacio De; López Ruiz, Nuria; Escobedo Araque, Pablo; Palma López, Alberto José; Capitán Vallvey, Luis Fermín; Erenas Rodríguez, Miguel María; Pérez de Vargas Sansalvador, Isabel María Passive fluid flow is not sufficient to meet new analytical requirements, therefore further research is needed in the field of flow control in order to improve the application of microfluidic systems. In this work, stimuli-sensitive materials have been studied to act as barriers and repositories to be integrated in µPADs. Poly(N-isopropylacrylamide) (p-NIPAM) has been studied to act as a reservoir and flow retardant. As a reservoir, the swelling/de-swelling behaviour has been characterised as a function of temperature, kinetics, reservoir size and the influence of pH. As a flow retardant, a p-NIPAM ionogel was used to significantly slow down the flow and even stop it. This is very useful for preventing the mixing of reagents until a certain point in time or for controlling where the mixing occurs. The ionogel volume and the delay time were optimised. As proof of concept, they were used in a colorimetric µPAD for nitrite determination based on the Griess chemistry. The results demonstrate the feasibility of integrating the developed stimulus-sensitive materials in µPADs, enabling new applications where these tools are required. This research was funded by Spanish MCIN/AEI/10.13039/501100011033/with project PID2022-138727OB-I00. The project was partially supported by European Regional Development Funds “ERDF A way of making Europe”. Funding for open access charge: Universidad de Granada / CBUA. https://hdl.handle.net/10481/111401 Valorization of wheat-derived pharmaceutical waste via sustainable NADES-based extraction and untargeted bioactive profiling Ciriaco, Lidia; Carbonell Rozas, Laura; Narváez, Alfonso; Maglione, Barbara; Izzo, Luana; Grieco, Paolo; García Campaña, Ana María The production of the aqueous extract of wheat (Triticum vulgare), known for its tissue repair properties, generates significant solid waste, with no identified reuse. Traditional extraction techniques, using organic solvents, are widely used for their efficiency, but present disadvantages, as long extraction times and high consumption of organic solvents, often toxic and environmentally harmful. To overcome these limitations and reduce environmental impact, new-generation solvents, such as natural deep eutectic solvents (NADES), have recently emerged. This study investigates the extraction efficiency of NADES for recovering bioactive compounds from wheat-based waste using both targeted and untargeted analytical approaches. Eight NADES formulations with varying physicochemical properties (pH, polarity, and viscosity) were evaluated. The extraction efficiency was assessed through ferulic acid recovery analysis by UHPLC-Q-ToF-HRMS. The highest recovery was achieved using a NADES composed of betaine:1,3-butanediol:water (molar ratio, 1:3:10.6), attributed to its moderate pH, low viscosity, and water content. The key parameters of the ultrasound-assisted extraction were optimized using Response Surface Methodology (RSM). Results showed that the extraction yield was comparable to that obtained using a conventional hydroalcoholic mixture, while non-targeted analysis revealed the presence of different bioactive compounds depending on the extraction solvent. The optimized method was assessed for greenness and applicability through AGREEprep and BAGI metrics, compared with hydroalcoholic extraction approaches. This study highlights the potential of wheat-based waste as a valuable source of ferulic acid and other bioactive compounds, demonstrating the feasibility of NADES as a sustainable alternative to traditional solvents for producing ready-to-use extracts suitable for nutraceutical and pharmaceutical applications. https://hdl.handle.net/10481/111365 Fermentation-driven biotransformation of a carob-based yogurt alternative enhances antioxidant responses in human keratinocytes Caponio, Mario; Gómez Caravaca, Ana María; Verardo, Vito; Pinto, Daniela; Mondadori, Giorgia; Carofiglio, Vito Emanuele; Centrone, Domenico; Verni, Michela; Giuseppe Rizzello, Carlo Thanks to its ecological and economic advantages, as well as numerous beneficial effects on human health, carob-based fermented products are ideal candidates for the development of functional foods that can also contribute to the Sustainable Development Goals. In this study, a plant-based yogurt alternative was developed using carob and rice flour fermented with selected lactic acid bacteria. All the strains showed good pro-technological performances (fast acidification and growth up to 9 log cfu/g), as well as the ability to increase DPPH radical scavenging activity compared to unfermented control (on average 74 against 61 %), but Lactiplantibacillus plantarum 18S9 was selected as the optimal starter. HPLC-ESI-Q/TOF profiling revealed major fermentation-driven modifications in phenolic composition, including the generation of pyrogallol. Whereas assays on human keratinocytes showed that both unfermented and fermented gurts mitigated H₂O₂-induced oxidative stress, with G-18S9 eliciting stronger regulation of genes encoding for enzymes involved in oxidative stress protection (SOD2 and HMOX-1). These findings provide supporting evidence linking microbial biotransformation of carob phenolics to improved antioxidant defenses in human cells, underscoring the potential of fermentation to enhance the functional value of underutilized plant ingredients and highlighting a promising route for producing high-value, sustainable yogurt alternatives that combine technological stability, consumer acceptability, and health-promoting properties. https://hdl.handle.net/10481/111261 Antibacterial activity of isolated phenolic compounds from cranberry (Vaccinium macrocarpon) against Escherichia coli Rodríguez Pérez, Celia; Quirantes-Piné, Rosa; Uberos Fernández, José; Jiménez-Sánchez, Cecilia; Peña, Alejandro; Segura Carretero, Antonio Phenolic compounds from a cranberry extract were isolated in order to assess their contribution to the antibacterial activity against urophatogenic strains of Escherichia coli (UPEC). With this purpose, a total of 25 fractions from a cranberry extract were isolated using semipreparative high performance liquid chromatography (HPLC) and characterized based on the results obtained by reversed-phase HPLC coupled to mass spectrometry detection. Then, the effect on UPEC surface hydrophobicity and biofilm formation of the cranberry extract as well as the purest fractions (a total of 13) was tested. As expected, the whole extract presented a powerful antibacterial activity against UPEC while the selected fractions presented different behavior. Myricetin and quercitrin significantly decreased (p < 0.05) E. coli biofilm formation compared with the control, while dihydroferulic acid glucuronide, procyanidin A dimer, quercetin glucoside, myricetin and prodelphinidin B led to a significant decrease on the surface hydrophobicity compared with the control. The results suggest that apart from procyanidins, other compounds, mainly flavonoids, can act against E. coli biofilm formation and also modify UPEC surface hydrophobicity in vitro, one of the first steps of adhesion. This work was supported by the projects AGL2011-29857-C03-02, P09-CTS-4564, P10-FQM-6563, and P11-CTS-7625 (Andalusian Regional Government Council of Innovation and Science) and PI070274 (Carlos III Institute of Health for Clinical Research, Madrid, Spain). The authors are grateful to the Spanish Ministry of Economy and Competitiveness (MINECO) for a FPU fellowship AP2010-1551 (Spanish Ministry of Science and Innovation) (C. Rodríguez-Pérez), and a grant “Personal técnico de apoyo” PTA2012-6956-E (R. Quirantes-Piné).