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[ES] La presente tesis se centra en la síntesis, caracterización, evaluación y aplicación en ensayos de lateral-flow de sensores moleculares, así como, de distintos sistemas híbridos orgánicos-inorgánicos basados en nanopartículas de sílice mesoporosa (MSNs) capaces de producir una respuesta fluorogénica ante la presencia de estímulos exógenos específicos como serían las drogas de abuso para su detección en diferentes medios competitivos. En el primer capítulo, se establece una visión general de los tipos de drogas de abuso existentes, así como, sus principales características y la importancia del desarrollo de nuevos métodos para detectarlas. Además, se presenta una visión general del campo de la nanotecnología, y su potencial aplicación como herramientas multifuncionales en el campo de los sensores, así como, una descripción general de sistemas de detección basados en complejos de metales de transición. A continuación, en el segundo capítulo se enumeran los principales objetivos generales a conseguir durante el desarrollo de la presente tesis doctoral. En el tercer capítulo se presenta un nanodispositivo para la detección fluorimétrica del estupefaciente 25I-NBOMe en golosinas. El sistema consta de MSNs cargadas con un fluoróforo y funcionalizadas en su superficie externa con un derivado de serotonina. Finalmente, los poros son bloqueados completamente por la interacción del derivado de serotonina anclado en la superficie con el anticuerpo del receptor 5-HT2A. La respuesta obtenida con el nanosensor es muy selectiva y con límites de detección bajos. En el cuarto capítulo se llevó a cabo la preparación y caracterización de un nanosensor para la detección fluorogénica selectiva y sensible de 3,4-metilendioxipirovalerona (MDPV), comúnmente conocida como droga caníbal. El nanodispositivo está basado en MSNs cargadas con un colorante fluorescente (rodamina B), y funcionalizadas en su superficie externa con un derivado de dopamina, que interactúa específicamente con el transportador de dopamina (DAT), bloqueando los poros. En presencia de MDPV, se produce la inhibición del reconocimiento entre el derivado de dopamina y el DAT que se desprende consecuentemente de las MSNs, provocando la liberación de rodamina B y permitiendo la detección de la droga. El nanodispositivo se ha empleado para la detección de MDPV en muestras de saliva y plasma sanguíneo. El quinto capítulo muestra el diseño de una sencilla tira portátil de doble canal usando nanomateriales híbridos para la detección in situ en muestras de saliva de escopolamina y MDPV, empleando un dispositivo smartphone. El nanosensor se basa en MSNs cargadas con un colorante fluorescente (rodamina B) y con la superficie externa funcionalizada con betanecol (agonista del receptor muscarínico de acetilcolina M2/CM2 (M2-AChR)). Al añadir el receptor M2-AChR se produce el tapado de los poros debido a la interacción específica con el derivado de betanecol. En el sexto capítulo se presenta un sensor molecular para la detección de GHB en bebidas alcohólicas, basado en un complejo de Cu2+ coordinado con un ligando tetradentado y un colorante fluorescente, cumarina 343. El mecanismo de detección se basa en un ensayo de desplazamiento del indicador (IDA). Este sistema se incorporó a una tira reactiva en un ensayo de lateral-flow. Por último, en el capítulo 7 se presentan las conclusiones generales. Los estudios realizados mostraron que estas sondas proporcionan excelentes ventajas sobre las técnicas analíticas tradicionales, tales como su simplicidad química, facilidad de uso, respuestas rápidas adecuadas para la detección in situ en tiempo real haciendo que la aplicación de estos sistemas suponga un prometedor avance para la detección precoz de casos de sumisión química o de adulteración de muestras con drogas de abuso difícilmente detectables., [CA] La present tesi se centra en la síntesi, caracterització, avaluació i aplicació en assajos tipus lateral-flow de sensors moleculars, així com, de diferents sistemes híbrids orgànics-inorgànics basats en nanopartícules de sílice mesoporosa (MSNs) capaços de produir una resposta fluorogénica davant la presència d'estímuls exògens específics com serien les drogues d'abús per a la seua detecció en diferents medis competitius. En el primer capítol, s'estableix una visió general dels tipus de drogues d'abús existents, així com, les seues principals característiques i la importància del desenvolupament de nous mètodes per a detectar-les. A més, es presenta una visió general del camp de la nanotecnologia, i la seua potencial aplicació com a eines multifuncionals en el camp dels sensors, així com, una descripció general de sistemes de detecció basats en complexos de metalls de transició. A continuació, en el segon capítol s'enumeren els principals objectius generals a aconseguir durant el desenvolupament de la present tesi doctoral. En el tercer capítol es presenta un nanodispositiu per a la detecció fluorimètrica de l'estupefaent 25I-NBOMe en llepolies. El sistema consta de MSNs carregades amb un fluorofore (rodamina B) i funcionalitzades en la seua superfície externa amb un derivat de serotonina. Finalment, els porus són bloquejats completament per la interacció del derivat de serotonina ancorat a la superfície amb l'anticòs del receptor 5-HT2A que actua com a porta molecular. La resposta obtinguda es molt selectiva i amb limits de detecció baixos. En el quart capítol es va dur a terme la preparació i caracterització d'un nanosensor híbrid orgànic-inorgànic per a la detecció fluorogénica selectiva i sensible de 3,4-metilendioxipirovalerona (MDPV), comunament coneguda com a droga caníbal. El nanodispositiu està basat en MSNs carregades amb un colorant fluorescent (rodamina B), i funcionalitzades en la seua superfície externa amb un derivat de dopamina, que interactua específicament amb el transportador de dopamina (DAT), bloquejant els porus. El nanodispositiu ha estat utilitzat amb exit per a detectar MDPV en mostres de saliva i plasma sanguini. En el cinqué capítol s'ha dissenyat una senzilla tira portàtil de doble canal usant nanomaterials híbrids per a la detecció in situ en mostres de saliva de escopolamina i MDPV. La detecció de aquestes drogues en saliva es du a terme mitjançant la utilització d'un dispositiu smartphone. El nanosensor es basa en MSNs carregades amb un colorant fluorescent (rodamina B) i amb la superfície externa functionalitzada amb un derivat de betanecol (agonista del receptor muscarínic d'acetilcolina M2/CM2 (M2-AChR)). En presencia de M2-AChR es tapen els porus a causa de la interacció específica amb el derivat de betanecol. En el sisé capítol es presenta un sensor molecular per a la detecció de GHB en begudes alcohòliques, basat en un complex de Cu2+ coordinat amb un lligand tetradentat i un colorant fluorescent, cumarina 343. El mecanisme de detecció es basa en un assaig de desplaçament de l'indicador (IDA). Aquest sistema es va incorporar a una tira reactiva en un assaig lateral-flow. Finalment, en el capítol setè es presenten les conclusions generals. Els estudis realitzats van mostrar que aquestes sondes (que poden ser simples molècules o sistemes més sofisticats que involucren biomolècules en materials híbrids orgànic-inorgànics) proporcionen excel·lents avantatges sobre les tècniques analítiques tradicionals, com son la seua simplicitat química, facilitat d'ús, respostes ràpides i adequades per a la detecció in situ en temps real fent que l'aplicació d'aquests sistemes supose un prometedor avanç per a la detecció precoç de casos de submissió química o d'adulteració de mostres amb drogues d'abús difícilment detectables., [EN] This PhD thesis focus on the synthesis, characterisation, evaluation and application in lateral-flow assays of molecular sensors, as well as different hybrid organic-inorganic systems based on mesoporous silica nanoparticles (MSNs) able to generate a fluorogenic response in the presence of specific exogenous stimuli such as abuse drugs for their detection in different competitive environments. In the first chapter, an overview about the different types of abuse drugs is given, as well as their main characteristics and the importance of new detection methods. In addition, a general view relate to metal complexes as sensor and nanotechnology is presented, and their potential application as multifunctional tools in the field of sensors. Then, the second chapter describes the main general objectives to be achieved during the development of this PhD thesis. The third chapter presents a nanodevice for the fluorimetric detection of 25I-NBOMe in candies. The system consists of MSNs loaded with a fluorophore (rhodamine B) and functionalised on their external surface with a serotonin derivative. Finally, the pores are completely capped by the interaction of the surface-anchored serotonin derivative with the 5-HT2A receptor antibody acting as a molecular gate. The response obtained with the nanosensor is quite selective and with low detection limits. In the fourth chapter, the preparation, and characterisation of a hybrid organic-inorganic nanosensor for the highly selective and sensitive fluorogenic detection of 3,4-methylenedioxypyrovalerone (MDPV), commonly known as cannibal drug, was carried out. The nanodevice is based on MSNs loaded with a fluorescent reporter (rhodamine B) and functionalised on their outer surface with a dopamine derivative, which specifically interacts with the dopamine transporter (DAT), capping the pores. The nanosensor was successfully used for MDPV detection in saliva and blood plasma samples. In the fifth chapter, a straightforward portable dual-track strip using nanomaterials has been designed for in situ in saliva samples and simultaneous detection of scopolamine and MDPV. Detection of both drugs in saliva samples was achieved by quantifying the released dye using a smartphone device. The nanosensor for MDPV detection is based on MSNs loaded with a fluorescent dye (rhodamine B) and a bethanechol derivative (an agonist of the muscarinic acetylcholine receptor M2/CM2 (M2-AChR)) grafted onto the external surface of the nanoparticles. Pores were capped after addition of M2-AChR due to its preferential coordination with the grafted bethanechol. The sixth chapter presents a molecular sensor for the GHB detection in alcoholic beverages, based on a Cu2+ complex coordinated with a tetradentate ligand and a fluorescent dye, coumarin 343. The detection mechanism is based on an indicator displacement assay (IDA). This system was incorporated into a test strip in a lateral-flow assay. Finally, general conclusions are presented in chapter seven. The studies performed showed that these probes (which can be from simple molecules to more sophisticated systems involving biomolecules in organic-inorganic hybrid materials) provide excellent advantages over traditional analytical techniques, such as their chemical simplicity, ease of use, rapid responses suitable for real-time in situ detection whereby the application of these systems is a promising advance for the early detection of chemical submission cases or adulteration of samples with hardly detectable abuse drugs.

Progress in the design of functional perovskite oxides relies on advances in density functional theory (DFT) methods to efficiently and effectively model complex systems composed of several transition-metal ions. This work reports the application of DFT methods to investigate the electronic structure of the YSr2Cu2FeO8−δ (0 < δ < 1) family in which the insulating, metal, or superconducting behaviors and even anion conductivity can be tuned by modifying the oxygen content. In particular, we assess the performance of the generalized gradient approximation (GGA), its Hubbard-U correction (GGA + U), and the strongly constrained and appropriately normed (SCAN) to model the metallic (idealized YSr2Cu2FeO8) and insulating (idealized YSr2Cu2FeO7) phases of the system. The analysis of the DFT results is supported by DC resistivity measurements that denote the metal character of the synthesized YSr2Cu2FeO7.86 and the semiconducting character of YSr2Cu2FeO7.08 prepared under reducing conditions. In addition, the band gap of YSr2Cu2FeO7.08, in the range of 0.73−1.2 eV, has been extracted from diffuse reflectance spectroscopy (DRS). While the three methodologies (GGA, GGA + U, SCAN) permit the reproduction of the crystal structures of the synthetized oxides (determined here in the case of YSr2Cu2FeO7.08 by neutron powder diffraction (NPD)), the SCAN emerges as the only one capable to predict the basic electronic and magnetic properties across the YSr2Cu2FeO8−δ (0 < δ < 1) series. The picture that emerges for the metal (δ = 0) to insulating (δ = 1) transition is the one in which oxygen vacancies contribute electrons to the filling of the Cu/Fe-3dx2−y2 states of the conduction band. These results validate the SCAN functional for future DFT investigations of complex functional oxides that combine severaltransition metals.

The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the β → α pressureinduced phase transition in SnMoO4 and the substitution process of Mo6+ by W6+ in SnMo1−xWxO4 solid solutions (x = 0-1). Special attention is paid to discriminating the role of the lone pair Sn2+ cation from the structural distortive effect along the Mo/W substitution process, which is crucial to disentangle the driven force of the transition phase. Furthermore, the reverse α → β transition observed at high temperature in SnWO4 is rationalized on the same basis as a negative pressure effect associated with a decreasing of W6+ percentage in the solid solution. This work opens a versatile chemical approach in which the types of interactions along the formation of solid solutions are clearly differentiated and can also be used to tune their properties, providing opportunities for the development of new materials.

Covalent functionalization of multi-walled carbon nanotubes (MWCNTs) and oxidized MWCNTs (o-MWCNTs) with chlorodiphenylphosphine (Ph2PCl) has been studied by cyclic voltammetry in organic medium. Depending the upper potential limit used in the electrochemical functionalization, different amount of phosphorus incorporation n is obtained, as result of the formation of radical species during the electrochemical oxidation of the Ph2PCl. The electrochemical oxidation of Ph2PCl promotes the covalent attachment of diphenylphosphine-like structure on the carbon nanotube surface. At the same time, the incorporation of Cl on the carbon nanotubes is observed during the functionalization. Furthermore, the presence of oxygen surface groups on the MWCNTs provides a favorable attachment of the Ph2P ∙ + species, which has promoted preferentially the formation of C-P bonds, whereas the amount of Cl is reduced. The authors would like to thank MINCIN (PID2019-105923RB-I00) for the financial support.

[EN] Monitoringreinforced concrete structures (RCS) is essential to ensure their service life. Monitoring the parameters associated with deterioration processes can be key for proactive maintenance. A gap exists between engineering practices and sensor technology innovation in the construction field, which prevents more development and widespread applications of using voltammetric sensors and a multivariate analysis. This review demonstrates the effectiveness of voltammetric stainless steel (SS) sensors, plus a principal component analysis (PCA), to detect the aspects involved in corrosion processes; e.g. concrete carbonation or presence of chlorides. Sensors were embedded in different concrete mixtures and exposed to different conditions. Electrochemical techniques were applied. Then the results were analysed by a PCA, which defined the durability control model. This model is able accurately detect the concrete state, which is verified by the model¿s validation. This novel system helps to sustainably preserve the service life of RCS., This work was supported by the Universitat Politecnica de Valencia, Ayudas a Primeros Proyectos de Investigacion (PAID-06-18) through the Lengua Electronica Voltametrica para el Control de Durabilidad en Hormigones under Grant SP20180245. The work of Ana Martinez Ibernon was supported by the Spanish Ministry of Science and Innovation for the Predoctoral Scholarship under Grant FPU 16/00723. The associate editor coordinating the review of this article and approving it for publication was Prof. Rosario Morello.

In this work, the impregnation order of the second metal and the catalytic performance of low loaded Pd and Ni bimetallic catalysts were studied using different supports (γ-Al2O3, γ-Al2O3–Mg, CaCO3 and RX3). These catalysts were assessed in the selective hydrogenation of 1-pentyne and the purification of a mixture of 1-pentene/1-pentyne 70/30 vol%. The results showed that the synthesized catalysts were active and very selective (≥ 85%) for obtaining the desired product (1-pentene). Different adsorbed species (–C≡C– and –C=C–) were observed on the bimetallic surface using in situ DRIFT analysis, which can be responsible of the high selectivity reached. The order of impregnation of the metals modifies the electronic and geometric properties of the synthesized catalysts. The best catalytic performance was obtained when the Pd is impregnated in second place: Ni–Pd/Support. The results show that the synthesized bimetallic catalysts have favorable properties and are promising for olefin purification reactions. The financial support provided by Universidad Nacional del Litoral (UNL, CAI+D Grants), Consejo Nacional de Investigaciones Científicas y Técnicas and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT, PICT Grants) are acknowledged. L. Garcia thanks Minciencias for the scholarship for Doctorates abroad 2019 (Call 860).

Guefoams (guest-containing foams) are a new-class of open-cell cellular materials that extend the properties of conventional foams by incorporating guest phases that convert them into multifunctional materials. This manuscript describes the development of pitch-derived composite guefoams that contain two types of inclusions: iron nanoparticles embedded in the cellular skeleton and activated carbon particles as guest phases. The activated carbon particles significantly increase the specific surface area and gas adsorption capacity. When these materials are exposed to low-intensity magnetic fields, the iron nanoparticles confer a high magneto-inductive capacity that enables ultrafast heating and rapid desorption of adsorbed species. The ability of these materials to act as preconcentrators for volatile organic compounds (VOCs) is demonstrated in this work using toluene as a proof of concept. The Guefoams developed here have greater preconcentration capabilities than current state-of-the-art systems while also being significantly more energy efficient due to the magnetic induction controlled desorption process. This unparalleled blend of properties makes these guefoams a valuable tool for energy-efficient VOCs management. This work was supported by the Spanish Agencia Estatal de Investigación (AEI), the Spanish Ministry of Science and Innovation, and the European Union (FEDER and NextGenerationEU funds) [grants MAT2016-77742-C2-2-P and PDC2021-121617-C21]. The author would also like to acknowledge the financial support received from the Conselleria d'Innovació, Universitats, Ciència, i Societat Digital of the Generalitat Valenciana through grant GVA-COVID19/2021/097.

Conocer los fundamentos teóricos de la química inorgánica es esencial para comprender los conceptos y principios esenciales de esta rama de la química, que se enfoca en el estudio de los elementos y compuestos inorgánicos; proporcionando una base teórica sólida para el estudio de otras áreas de esta ciencia. "Fundamentos Teóricos de Química Inorgánica", además de temas clave de la química inorgánica, como la teoría del enlace de valencia y la química de los elementos, también cubre temas importantes como la estructura de la materia, la teoría cuántica, la estequiometría y la clasificación de las reacciones químicas. Asimismo, se destaca la inclusión de temas relacionados con la medición de las propiedades de la materia, la descripción de los sistemas dispersos, entre otros. El objetivo de este libro es brindar una base sólida de conocimientos en química inorgánica, que permita al lector comprender los principios y fundamentos teóricos que rigen esta disciplina, con un enfoque claro y didáctico. El libro proporciona un excelente recurso tanto para estudiantes como para docentes. Razón por la que, "Fundamentos Teóricos de Química Inorgánica" es una obra esencial para aquellos que deseen profundizar en el conocimiento de la química inorgánica y comprender mejor sus conceptos fundamentales

A combination of omics techniques (transcriptomics and metabolomics) has been used to elucidate the mechanisms responsible for the antitumor action of a nanosystem based on a Ag core coated with mesoporous silica on which transferrin has been anchored as a targeting ligand against tumor cells (Ag@MSNs-Tf). Transcriptomics analysis has been carried out by gene microarrays and RT-qPCR, while high-resolution mass spectrometry has been used for metabolomics. This multi-omics strategy has enabled the discovery of the effect of this nanosystem on different key molecular pathways including the glycolysis, the pentose phosphate pathway, the oxidative phosphorylation and the synthesis of fatty acids, among others. Graphical Abstract

[ES] En la presente tesis doctoral se exponen los resultados obtenidos en el desarrollo inicial de un sistema multisensor, tipo lengua electrónica voltamétrica, para el control de la durabilidad de las estructuras de hormigón armado (EHA). Aunque los sistemas multisensores son ampliamente utilizados en diferentes ámbitos, como el del medio ambiente o de la industria alimentaria, su uso en las EHA es novedoso. Igualmente, resulta novedosa la utilización de sensores voltamétricos que, como se demuestra en esta tesis, son de gran eficacia en el análisis de parámetros relacionados con el deterioro del hormigón armado, mejorándose los modelos de durabilidad obtenidos a través de sensores potenciométricos. Todo ello, sin ser aumentada de manera inabordable la complejidad electrónica y computacional del sistema. El prototipo de lengua electrónica diseñado es un sistema de sensores híbridos que consta de cuatro electrodos de trabajo (Au, Ag, Ni e INOX). Se dice que es híbrido porque se usan técnicas tanto voltamétricas (voltametría cíclica) como impedimétricas (espectroscopia de impedancia). Se han utilizado metales nobles (Au y Ag), metales no nobles (Ni) y aleaciones de alta durabilidad (acero inoxidable) con el fin de obtener un comportamiento electroquímico más variado. En la fase previa al desarrollo del sistema se seleccionaron los metales a utilizar en los sensores que formarían parte del sistema multisensor. Para ello se realizó un número ingente de ensayos con distintos metales (Ir, Rh, Pt, Au, Ag, W, Ni y INOX), tanto en disolución (simulando las condiciones de disolución de poro del hormigón), como en hormigón, con el fin de ser seleccionados aquellos metales de cuya respuesta se pudiera extraer una mayor información. Una vez finalizada la fase previa se estudió la respuesta aislada de cada uno de los metales seleccionados (Au, Ag, Ni e INOX), dividiéndose el estudio en 3 fases: ¿ Fase 1. Estudio en disolución: se analizaron los procesos que tienen lugar sobre la superficie del electrodo en disoluciones que simulaban distintas circunstancias que se pueden dar en el hormigón (variación de la disponibilidad de O2, variación del pH y presencia del anión cloro). Los resultados obtenidos se compararon con los encontrados en literatura. ¿ Fase 2. Estudios hechos con el sensor embebido en hormigones convencionales sin adiciones. Se embebieron sensores voltamétricos en hormigones convencionales de distinta relación agua/cemento. Seguidamente, se analizaron las probetas bajo distintas circunstancias que tuvieran influencia en el desencadenamiento y cinética de los procesos de corrosión como son: o Variaciones en la disponibilidad de O2 y H2O. o Carbonatación del hormigón. o Presencia de Cl-. ¿ Fase 3. Se desarrollaron modelos que permitieran identificar variaciones en parámetros relacionados con el deterioro del hormigón armado o estimar y predecir el parámetro de interés. Terminado el estudio de la respuesta aislada de los cuatro sensores, se procedió a evaluar la respuesta cruzada de los sensores siguiendo los protocolos propios de las lenguas electrónicas. Tras analizar y comparar las respuestas aisladas y cruzadas de los sensores, se propuso una rutina de trabajo que en un futuro ayude a optimizar los recursos, tanto operacionales como de fabricación, utilizados en el sistema. Para finalizar, se hizo un estudio inicial para tratar de mejorar la autonomía del sistema, evaluando el efecto producido al simplificar la configuración de celda, reduciendo el número de electrodos de tres a dos., [CA] En la present tesi doctoral s'exposen els resultats obtinguts en el desenvolupament inicial d'un sistema multisensor, tipus llengua electrònica voltamètrica, pel control de la durabilitat de les estructures de formigó armat (EFA). Encara que l'ús d'aquest tipus de sistema està molt expandit en l'àmbit del medi ambient i de la indústria alimentària, el seu ús en les EFAs és molt nou. Igualment, resulta nova la utilització de sensors voltamètrics, que com és demostra en aquesta tesi, són de gran eficàcia en la determinació de les condicions del formigó armat, millorant-se considerablement els models de durabilitat obtinguts mitjançant sensors potenciomètrics. Tot això, sense augmentar la complexitat electrònica i computacional del sistema d'una forma inabordable. El prototip dissenyat de llengua electrònica és un sistema de sensors híbrids compost per quatre elèctrodes de treball (Au, Ag, Ni i acer inoxidable). Es diu que és híbrid perquè en el sistema de sensors s'utilitzen tècniques voltamètriques i impedimètriques. S'han utilitzat metalls nobles (Au i Ag), metalls no nobles (Ni) i aliatges d'alta durabilitat (acer inoxidable). Amb la finalitat d'obtindre un comportament electroquímic més variat. En la fase prèvia al desenvolupament del sistema, es van seleccionar els metalls a utilitzar en els sensors que formarien part del sistema multisensor. Per a això es va realitzar una quantitat ingent d'assajos amb diferents metalls (Ir, Rh, Pt, Au, Ag, W, Ni i acer inoxidable), tant en dissolució com en formigó, amb l'objectiu de seleccionar aquells metalls dels quals es poguera aconseguir més informació amb la seua resposta. Una vegada finalitzada aquesta fase prèvia, es va estudiar la resposta aïllada de cadascun dels metalls seleccionats (Au, Ag, Ni i acer inoxidable). L'estudi es va dividir en tres fases: ¿ Fase 1. Estudis en dissolució: es van analitzar els processos duts a terme sobre la superfície de l'elèctrode en dissolucions que simulaven diferents circumstàncies que es poden donar en el formigó (variació de la disponibilitat d' O2, variació de pH i presència de l'anió clor). Els resultats obtinguts es van comparar amb els trobats en la literatura. ¿ Fase 2. Estudis fets amb els sensors embeguts en formigó: es van embeure els sensors voltamètrics en formigons convencionals de diferent relació aigua/ciment i sense adicions. A continuació, es van analitzar les provetes sota diferents circumstàncies que tingueren influència en el desencadenament i cinètica dels processos com són: o Variacions en la disponibilitat d' O2 i H2O. o Carbonatació del formigó. o Presencia de Cl-. ¿ Fase 3. Desenvolupament de models que possibiliten identificar variacions en paràmetres relacionats amb el deteriorament del formigó armat o estimar i predir el paràmetre d'interès. Finalitzat l'estudi de la resposta aïllada dels quatre sensors, es va avaluar la resposta creuada mitjançant protocols propis de les llengües electròniques (PCA i PLS). Després d'analitzar i comparar les respostes aïllades i creuades dels sensors, es va proposar una rutina de treball que un futur ajude a optimitzar els recursos, tant operacionals com de fabricació, utilitzats al sistema. Per acabar, es va fer un estudi inicial per a tractar de millorar l'autonomia del sistema, avaluant l'efecte produït al simplificar la configuració de cel·la, reduint el nombre d'elèctrodes de tres a dos., [EN] In this thesis the results obtained in the development of a multisensor system, known as electronic voltametric tongue, for the reinforcement concrete structures' (RCS) durability control are exposed. Although the use of this multisensor system is widespread in different fields such as: the food industry and environmental control, its use in RCS monitoring is very novel. It is equally novel the use of voltametric sensors, this kind of sensors are very efficient in determining concrete conditions, improving the durability models obtained through potentiometric sensors, all without overly increasing the system's electronic and computational complexity The electronic tongue prototype designed is a hybrid sensor system made up of four working electrodes (Au, Ag, Ni and stainless steel). It has been referred to as hybrid because in the system voltametric and impedimetric electrochemical techniques are used. Noble metals (Au and Ag), non-noble metals (Ni) and high-durability alloys (stainless steel) have also been used with the purpose of achieving a more varied electrochemical behaviour. In the previous development phase of the system, the metals involved in the development of the electronic tongue were selected. In order to do this, a variety of tests with different metals were performed (Ir, Rh, Pt, Au, Ag, W, Ni and SS), in both dissolution (different concrete pore solution conditions were simulated) and hardened concrete. This allowed us to choose the metals which responses contained the most information. The next steps focused on the study of the selected sensors isolated response: ¿ Phase 1: simulation of concrete pore solution in dissolution systems. The results were compared with those already existing in the bibliography. ¿ Phase 2: studies with the sensors embedded in different standard concretes without additions. The samples were tested in different conditions involved in the rebars corrosion kinetics (variations in O2 and humidity availability, concrete carbonation and chlorides presence). ¿ Phase 3: Development of estimation models for the parameters of interest. After finishing the study of the isolated sensors' response, a cross-evaluation of their response was performed using typical protocols used in the electronic tongues (i.e. PCA and PLS). After analysing and comparing the isolated and crossed sensor's response, an optimized multisensory routine work was proposed which could, in the future, help optimize the resources used in the system. Finally, a study was carried out to improve the system's autonomy, in which the repercussion of the cell configuration simplification by means of the removal of the reference electrode was evaluated., La autora quiere expresar su agradecimiento al Ministerio de Educación, Cultura y Deporte por la beca predoctoral FPU 16/00723

Photoredox catalysis constitutes a very powerful tool in organic synthesis, due to its versatility, efficiency, and the mild conditions required by photoinduced transformations. In this paper, we present an efficient and selective photocatalytic procedure for the aerobic oxidative dehydrogenation of partially saturated N-heterocycles to afford the respective N-heteroarenes (indoles, quinolines, acridines, and quinoxalines). The protocol involves the use of new Ir(III) biscyclometalated photocatalysts of the general formula [Ir(C^N)2(N^N′)]Cl, where the C^N ligand is 2- (2,4-difluorophenyl)pyridinate, and N^N′ are different ligands based on the 2-(2′-pyridyl)benzimidazole scaffold. In-depth electrochemical and photophysical studies as well as DFT calculations have allowed us to establish structure−activity relationships, which provide insights for the rational design of efficient metal-based dyes in photocatalytic oxidation reactions. In addition, we have formulated a dual mechanism, mediated by the radical anion superoxide, for the above-mentioned transformations., We acknowledge the financial support provided by the Spanish Ministerio de Ciencia, Innovación y Universidades (RTI2018- 100709-B-C21 and CTQ (QMC)-RED2018-102471-T), Consejería de Educación de la Junta de Castilla y León and FEDER (BU087G19 and BU067P20), and Junta de Comunidades de Castilla-La Mancha-FEDER (JCCM) (grant SBPLY/19/ 180501/000260). I.E. acknowledges his fellowship to both the European Social Fund and Consejería de Educación de la Junta de Castilla y León (EDU/1100/2017). We are also indebted to J. Delgado, P. Castroviejo, and M. Mansilla (PCT of the Universidad de Burgos) for technical support, G. GarcíaHerbosa for providing us access to CV equipment, and J. V. Cuevas-Vicario for support with Gaussian.

Interzeolite transformation has been used to produce a novel family of hierarchical catalysts featuring excellent textural properties, strong acidity, and superior catalytic performance for the Friedel–Crafts alkylation of indole with benzhydrol, the Claisen–Schmidt condensation of benzaldehyde and hydroxyacetophenone, and the cracking of polystyrene. Intermediate solids of the FAU interzeolite transformation into BEA display both increased accessibility─due to the development of mesoporosity─and strong acidity─caused by the presence of ultrasmall crystals or zeolitic fragments in their structure. The use of surfactants allows for the development of the hierarchical catalysts with very narrow pore size distribution. The properties of interzeolite transformation intermediates (ITIs) can be fine-tuned simply by stopping the interconversion at different times. The authors thank the European Commission for funding through the H2020-MSCA-RISE-2019 program (Ref. ZEOBIOCHEM-872102) and the Spanish MINECO and AEI/FEDER, UE, through Project Ref. RTI2018-099504-B-C21. N.L. also acknowledges the University of Alicante support (UATALENTO17-05). M.J.M. thanks the Generalitat Valenciana for a PhD fellowship (GRISOLIAP/2020/165). Carlos A. Trujillo and Nelcari T. Ramírez M. express their gratitude to the Universidad Nacional de Colombia for providing physical and technical resources for this research also to Minciencias and Ecopetrol in the frame of Contract 0402-2013.

Introduction: Nano-based systems have received a lot of attention owning their particular properties and hence, have been proposed for a wide variety of biomedical applications. These nanosystems could be potentially employed for diagnosis and therapy of different medical issues. Although these nanomaterials are designed for specific tasks, interactions and transformation when administered to the human body affect their performance and behaviour. In this regard, bacteria and other cells have been presented as alternative nanocarriers. These microorganisms can be genetically modified and customized for a more specific therapeutic action and, in combination with nanomaterials, can lead to bio-hybrids with a unique potential for biomedical purposes. Areas covered: Literature regarding bacteria and cells employed in combination with nanomaterials for biomedical applications is revised and discussed in this review. The potential as well as the limitations of these novel bio-hybrid systems are evaluated. Several examples are presented to show the performance of these alternative nanocarriers. Expert Opinion: Bio-hybrid systems have shown their potential as alternative nanocarriers as they contribute to a better performance than traditional nano-based systems. Nevertheless, their limitations must be studied, and advantages and drawbacks assessed before their application to medicine.

Se analiza un conjunto de tres discos de cerámica procedentes de los niveles del Hierro Antiguo de Peña Negra. Presentan diferentes acabados y estarían provistos de asas, por lo que deben interpretarse como tapaderas de grandes recipientes de almacenaje. Se ha realizado el estudio petrográfico y mineralógico mediante microdifracción de rayos X (µDRX). Los resultados indican que se trata de piezas de composición relativamente homogénea y de probable producción local, cocidas a baja temperatura. Se revisa el hallazgo de objetos similares en otros contextos del Hierro Antiguo, destacando los recuperados en el Noreste peninsular y el Valle del Ebro, donde además se localizan discos-tapadera realizados en yeso similares a dos ejemplares recuperados en Peña Negra, donde es un material frecuente empleado en la construcción y en la fabricación de objetos. A set of three ceramic discs from the Early Iron Age levels of Peña Negra are analysed. They exhibit differences in surface treatment and would have been fitted with handles, so they should be interpreted as lids of large storage vessels. Samples of each disc were studied by means of petrographic and mineralogical analysis (X-ray micro-diffraction, µDRX). Resulting data indicate that those are pieces of relatively homogeneous composition and that were probably locally produced, fired at low temperatures. The discovery of similar objects in other Early Iron Age contexts is reviewed, highlighting those recovered in the Northeast of the Iberian Peninsula and the Ebro Valley, where gypsum discs have also been found, similar to two examples found in Peña Negra. In this site, gypsum was commonly used as raw material in building activities and other crafts. Este trabajo se ha realizado en el marco del proyecto del Ministerio de Ciencia, Innovación y Universidades HAR2017-87495-P, “Fenicios e indígenas en el Sureste de la península ibérica: Bronce Final y Hierro Antiguo entre el Vinalopó y el Segura” y del proyecto de la Generalitat Valenciana AICO/2021/189, “Construyendo territorios entre el Bronce Final y el Ibérico Antiguo en los extremos de la Comunitat Valenciana (ConstrucTERR)”. El trabajo instrumental se ha financiado con una ayuda de la Fundación Palarq (Analíticas 2019), desarrollada en el marco de un convenio de colaboración con la Universidad de Alicante para la coordinación y desarrollo del proyecto “Estudio de investigación para llevar a cabo analítica de cerámica prehistórica” (FUNDACIONPALARQ1-19X). También con la Ayuda para la utilización de los Servicios Técnicos de Investigación del Vicerrectorado de Investigación y Transferencia de Conocimiento de la Universidad de Alicante (UAUSTI19-15). María Pastor Quiles es investigadora Juan de la Cierva-formación (FJC2019-039469-I) financiada por el Ministerio de Ciencia e Innovación y el Institut Català d’Arqueologia Clàssica. Miguel del Pino Curbelo disfruta de un contrato del programa Viera y Clavijo, financiado por la Universidad de Las Palmas de Gran Canaria.

[EN] Synthetic cathinones are a class of new psychoactive substances whose consumption has increased a lot and is widespread throughout the world. Thus, there is currently a need for rapid and simple detection of these drugs. In particular, detection of synthetic cathinones in oral fluid in drivers can be of great importance in preventing traffic accidents. Herein, we report two probes, based on BODIPY derivatives combined with Cu(ii), which are able to detect these drugs both in water and in oral fluid, by changes in color and fluorescence. The determined limits of detection for ephedrone (as a model drug) are lower than the usual concentrations in saliva after intake of this type of drug. The sensing mechanism seems to be related to the cathinone induced reduction of Cu(ii) to Cu(i) with concomitants changes in the BODIPY structure., We thank the Spanish Government, MCIN/AEI/10.13039/501100011033 and "ERDF A way of making Europe" (fund RTL2018-100910-B-C42), the Spanish Ministry of Health, Consumer Affairs and Social Welfare (Project 2020I040 PNSD 2020) and Generalitat Valenciana (PROMETEO 2018/024) for financial support. SCSIE (Universitat de Valencia) is gratefully acknowledged for all the equipment employed. NMR was registered at the U26 facility of ICTS "NAMBIOSIS" at the Universitat of Valencia.

High surface area mixed oxide 8.7% NiO-CeO2 nanoparticles (122 m2/g; 6–7 nm) were prepared using a reversed microemulsion method, and were tested for dry methane reforming (DRM). The catalytic activity of these nanoparticles remains stable under the severe conditions of DRM (700 °C), and they show better carbon resistance than conventional NiO-CeO2 catalysts prepared without control of the size. The activity and selectivity of nanoparticles and reference catalyst are similar, but nanoparticles reduce by 63% the accumulation of carbon during the DRM tests, which is a key feature for this reaction. XPS and H2-TPR suggest that the improved carbon resistance of the nanoparticles is the better interaction and cooperation between NiO and CeO2 mixed phases. In nanoparticles, the participation of cerium cations in the redox processes taking place during DRM stabilize cationic species of nickel. On the contrary, the catalyst prepared without control of the size suffered segregation of Ni during DRM reaction, and segregated Ni explains the higher catalytic formation of carbon. Project supported by the Generalitat Valenciana (Project PROMETEO/2018/076; ACA GRISOLIAP/2017/185; EBG APOSTD/2019/030), MINECO (CTQ2015-67597-C2-2-R), MICINN (PID2019-105960RB-C22) and European Union FEDER funds.

We present the first example of a silver double-tetranuclear cluster helicate [Ag4L2]2 obtained from a bisthiosemicarbazone ligand using electrochemical synthesis. This cluster helicate undergoes a rare desulfurization process in chloroform giving rise to a cationic silver dihelicate [Ag2(H2L)2]SO4. This is the first silver mediated desulfurization reaction., FEDER cofunded-grants: from Consellería de Cultura, Educación e Ordenación Universitaria, Xunta de Galicia, 2017 GRC GI-1682 (ED431C 2017/01), 2018 GRC GI-1584 (ED431C 2018/13), MetalBIO Network (ED431D 2017/01), Ministerio de Ciencia, Innovación y Universidades, METALBIO (CTQ2017-90802-REDT) and MultiMetDrugs (RED2018-102471-T).

In this study, water-soluble chitosan salts (chitosan amine sulfopropyl salts) were prepared from chitosan samples with different molecular weights and deacetylation degrees. These soluble-in-water polymer salts allowed us to produce, in an eco-friendly and facile method, silver nanoparticles (AgNPs) with better control on size and polydispersity, even at large silver concentrations than their corresponding chitosan sample. Chitosan salt-based materials (films and scaffolds) were analyzed in terms of antibacterial properties against Staphylococcus aureus ATCC23915 or Pseudomonas aeruginosa ATCC 27853. 3D scaffolds enhanced the effect of the chitosan-AgNPs combination compared to the equivalent films.

[ES] La inflamación es la respuesta natural y esencial del organismo a las señales derivadas del daño tisular o de una infección patógena. La inflamación, que se produce tras una lesión o infección, favorece el restablecimiento de la homeostasis al defender al huésped frente a patógenos exógenos y curar el tejido dañado. Suele producirse como una secuencia de acontecimientos, empezando por una fase de inducción rápida, que da lugar a una respuesta proinflamatoria, seguida gradualmente por una fase de resolución. Por lo tanto, la inflamación es crucial para la cicatrización de las heridas. Sin embargo, si esta respuesta bien orquestada se desregula, la inflamación puede volverse incontrolada o crónica, lo que en última instancia puede conducir al desarrollo y la progresión de diversas enfermedades, como el cáncer, la obesidad, la sepsis y las enfermedades cardiovasculares, neuronales y autoinmunes. Uno de los principales actores implicados en la inflamación crónica son los macrófagos, concretamente los macrófagos proinflamatorios de tipo M1. Estas células participan en la defensa del huésped destruyendo e ingiriendo sustancias nocivas para limitar los daños al organismo. Ejercen sus funciones proinflamatorias produciendo altos niveles de citocinas proinflamatorias, especies reactivas de oxígeno (ROS), óxido nítrico sintasa inducible (INOS), ciclooxigenasa (COX)-2 y especies reactivas de hidrógeno (H2O2). Por tanto, una de las formas de abordar el problema de la inflamación crónica podría ser intervenir sobre este tipo celular, aprovechando su función principal, la internalización de cuerpos extraños. Se han propuesto nuevos métodos de administración de fármacos basados en nanopartículas como sistemas adecuados de administración controlada, que pueden proporcionar una liberación sostenida y mejorar la especificidad de la diana, la semivida del fármaco y la difusión. En este sentido, las nanopartículas con movimiento activo (nanomotores) en respuesta a la catálisis de distintos combustibles, como el H2O2, son una herramienta prometedora para administrar fármacos en zonas enfermas de difícil acceso. Sin embargo, la mayoría de los nanodispositivos utilizan altas concentraciones de combustibles tóxicos y exógenos, lo que limita su aplicación 4 en el campo biomédico. Por eso, es interesante estudiar y desarrollar nanomotores autopropulsados por sustancias endógenamente presentes a altas concentraciones, como el H2O2, en las áreas terapéuticamente relevantes, [EN] Inflammation is the body’s natural and essential response to signals arising from tissue damage or pathogenic infection. Inflammation, which follows injury or infection, promotes the return of homeostasis by defending the host against exogenous pathogens and by healing damaged tissue. Inflammation usually occurs as a sequence of events, starting with a rapid induction phase, which leads to a pro-inflammatory response, gradually followed by a resolution phase. Therefore, inflammation is crucial to wound healing. However, if this wellorchestrated response is dysregulated, inflammation may become uncontrolled or chronic, which can ultimately lead to the development and progression of various inflammatory diseases, such as cancer, obesity, sepsis, cardiovascular, neuronal and autoimmune diseases. One of the main players involved in chronic inflammation are macrophages, specifically proinflammatory M1-type macrophages. These cells participate in host defence by destroying and ingesting harmful substances to limit damage to the organism. They exert their proinflammatory functions by producing high levels of proinflammatory cytokines, reactive oxygen species (ROS), inducible nitric oxide synthase (INOS), cyclooxygenase (COX)-2, and reactive nitrogen species (H2O2). Therefore, one of the ways to deal with the problem of chronic inflammation could be to intervene on this cell type, taking advantage of its main function, the internalisation of foreign bodies. Novel drug delivery methods based on nanoparticles have been proposed as suitable drug delivery systems, which can provide sustained release and improves target specificity, drug half-life and diffusion. In this sense, self-propelled nanoparticles with active movement (nanomotors) in response to catalysis of different fuels such as H2O2 are a promising tool to deliver drugs to hard-to-reach diseased areas. However, most nanodevices use high concentrations of toxic and exogenous fuels, which limits their application in the biomedical field. 6 For this reason, it is interesting to study and develop nanomotors powered by endogenously present substances at high level such as H2O2 in the therapeutically relevant areas

Osteoporosis is the most common type of bone disease. Conventional treatments are based on the use of antiresorptive drugs and/or anabolic agents. However, these treatments have certain limitations, such as a lack of bioavailability or toxicity in non-specific tissues. In this regard, pleiotrophin (PTN) is a protein with potent mitogenic, angiogenic, and chemotactic activity, with implications in tissue repair. On the other hand, mesoporous silica nanoparticles (MSNs) have proven to be an effective inorganic drug-delivery system for biomedical applications. In addition, the surface anchoring of cationic polymers, such as polyethylenimine (PEI), allows for greater cell internalization, increasing treatment efficacy. In order to load and release the PTN to improve its effectiveness, MSNs were successfully internalized in MC3T3-E1 mouse pre-osteoblastic cells and human mesenchymal stem cells. PTN-loaded MSNs significantly increased the viability, mineralization, and gene expression of alkaline phosphatase and Runx2 in comparison with the PTN alone in both cell lines, evidencing its positive effect on osteogenesis and osteoblast differentiation. This proof of concept demonstrates that MSN can take up and release PTN, developing a potent osteogenic and differentiating action in vitro in the absence of an osteogenic differentiation-promoting medium, presenting itself as a possible treatment to improve bone-regeneration and osteoporosis scenarios.

Bone diseases are a global public concern that affect millions of people. Even though current treatments present high efficacy, they also show several side effects. In this sense, the development of biocompatible nanoparticles and macroscopic scaffolds has been shown to improve bone regeneration while diminishing side effects. In this review, we present a new trend in these materials, reporting several examples of materials that specifically recognize several agents of the bone microenvironment. Briefly, we provide a subtle introduction to the bone microenvironment. Then, the different targeting agents are exposed. Afterward, several examples of nanoparticles and scaffolds modified with these agents are shown. Finally, we provide some future perspectives and conclusions. Overall, this topic presents high potential to create promising translational strategies for the treatment of bone-related diseases. We expect this review to provide a comprehensive description of the incipient state-of-the-art of bone-targeting agents in bone regeneration.

Surface microbial colonization and its potential biofilm formation are currently a major unsolved problem, causing almost 75% of human infectious diseases. Pathogenic biofilms are capable of surviving high antibiotic doses, resulting in inefficient treatments and, subsequently, raised infection prevalence rates. Antibacterial coatings have become a promising strategy against the biofilm formation in biomedical devices due to their biocidal activity without compromising the bulk material. Here, we propose for the first time a silver-based metal–organic framework (MOF; here denoted AgBDC) showing original antifouling properties able to suppress not only the initial bacterial adhesion, but also the potential surface contamination. Firstly, the AgBDC stability (colloidal, structural and chemical) was confirmed under bacteria culture conditions by using agar diffusion and colony counting assays, evidencing its biocide effect against the challenging E. coli, one of the main representative indicators of Gram-negative resistance bacteria. Then, this material was shaped as homogeneous spin-coated AgBDC thin film, investigating its antifouling and biocide features using a combination of complementary procedures such as colony counting, optical density or confocal scanning microscopy, which allowed to visualize for the first time the biofilm impact generated by MOFs via a specific fluorochrome, calcofluor.

La Tesis que aquí se presenta tiene como objetivo principal el diseño y estudio de las propiedades de una gran serie de compuestos que actúan como imanes moleculares. Estos compuestos consisten en polímeros de coordinación basados en el ligando anilato (C6O4X22-, siendo X = Cl o Br) con metales de transición como centros metálicos responsables del comportamiento magnético de dichos materiales. Así pues, en el Capítulo 1 se presenta una familia de compuestos isoestructurales entre sí con capas aniónicas en forma de panal abeja que se superponen de modo eclipsado originando canales hexagonales. En el interior de los canales hexagonales se alojan moléculas de disolvente que tienen un papel fundamental en la modulación del ordenamiento ferrimagnético observado en estos materiales. En el Capítulo 2, se ha preparado una familia de cuatro compuestos, similar a la de los anteriores, pero que difiere en la presencia de una molécula de disolvente coordinada a los iones Mn(II) de la red. En lo referente al magnetismo de estas redes, se observa que los iones metálicos presentan un ordenamiento de tipo ferrimagnético similar al de los compuestos del Capítulo 1. Este ordenamiento, sin embargo, se da a temperaturas inferiores a causa de la coordinación de la molécula de benzaldehído al ion Mn(II). En el Capítulo 3, se llevó a cabo un estudio similar para compuestos que presentan la pareja de metales Cu(II)/Cr(III) con la misma estructura que los pertenecientes a los capítulos anteriores. En estos materiales, sin embargo, se ha incorporado un tratamiento térmico a bajas presiones con el fin de eliminar las moléculas de disolvente presentes en la estructura. Además, también en estos materiales se ha observado que el ordenamiento ferrimagnético es sensible al disolvente presente en la estructura. En el Capítulo 4 de esta Tesis, se ha trabajado con las redes preparadas en los dos primeros capítulos. En concreto, se ha tratado de llevar a cabo la modificación postsintética del derivado del benceno presente en las estructuras. Además, en algunos de los productos obtenidos se ha probado el proceso de reversibilidad para restituir el compuesto original y en algunos otros se han realizado ensayos de evacuación a altas temperaturas y bajas presiones. En último lugar, en el Capítulo 5 se prepara una serie de compuestos con la molécula de fenacina como plantilla. Se ha podido ver en estos compuestos que existe un fenómeno de transferencia protónica entre las unidades que componen la capa catiónica y que depende, a su vez, de las distancias entre los bloques que forman la capa aniónica. Se ha podido ver que el magnetismo de los compuestos depende de la combinación de metales presentes en la red. Finalmente, en este mismo capítulo se ha llevado a cabo la reducción con naftalenuro de litio de los ligandos anilato en las redes de este tipo, conduciendo a variaciones importantes en sus propiedades magnéticas.

Producción Científica, Non-covalent interactions between sulfur centers and aromatic rings play important roles in biological chemistry. We examined here the sulfur–arene interactions between the fused aromatic heterocycle benzofuran and two prototype sulfur divalent triatomics (sulfur dioxide and hydrogen sulfide). The weakly-bound adducts were generated in a supersonic jet expansion and characterized with broadband (chirped-pulsed) time-domain microwave spectroscopy. The rotational spectrum confirmed the detection of a single isomer for both heterodimers, consistent with the computational predictions for the global minima. The benzofuran⋯sulfur dioxide dimer exhibits a stacked structure with sulfur closer to benzofuran, while in benzofuran⋯hydrogen sulfide the two S–H bonds are oriented towards the bicycle. These binding topologies are similar to the corresponding benzene adducts, but offer increased interaction energies. The stabilizing interactions are described as S⋯π or S–H⋯π, respectively, using a combination of density-functional theory calculations (dispersion corrected B3LYP and B2PLYP), natural bond orbital theory, energy decomposition and electronic density analysis methods. The two heterodimers present a larger dispersion component, but nearly balanced by electrostatic contributions., National Natural Science Foundation of China (No. 22273009), Ministerio de Ciencia e Innovación (MCIN-AEI) y FEDER (grant PID2021-125015NB-I00), FEDER - Junta de Castilla y León (grants INFRARED IR2021-UVa13 e IR2020-1-UVa02)

Polypyrrole (PPy) has been prepared by oxidative polymerization of pyrrole and used as a raw material for the preparation of N-doped activated carbons. Thus, PPy has been pyrolyzed at 900 °C and then activated with steam under different activation conditions (time and temperature). This has allowed for the preparation of activated carbons with different porosity development and nitrogen content, as well as distinctive distribution of nitrogen species. It has been observed that the presence of nitrogen functionalities favors water adsorption at low relative pressures but, at relative pressures higher than 0.5 it is determined by the porosity development. Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID2019-108453GB-C21) is gratefully acknowledged. Open access funding enabled and organized by Projekt DEAL.

The cleaning or removal of manganese stains on Cultural Heritage has not been much tested or successful so far. The aim of this article was to assess a new green cleaning gel for Mn-rich black-blue stains on different substrates. The black-blue stains were characterized at optical and chemical level through colour-related data, optical microscope, FTIR, XRF and XPS. Mn-stained granite found on historical churches at Vila Real (North of Portugal) and glass jars of Leclanché cells, belonging to the ISEP’s Museum (Portugal) collection, were the ideal case studies to test the efficiency of chitosan: thiourea dioxide (TD) cleaning gel. TD proved to be the best candidate to reduce insoluble manganese oxides, over Hydroxylamine Hydrochloride and Hydroxymethanesulfinic Acid. Cleaning assays performed on stained granite samples collected at a historical quarry and in situ application on stained granite churches allowed removal of the stains to a satisfactory level. Similar results were obtained on stained glass jars. This work was supported by BIO4MURAL–Biotechnology innovative solutions for the removal of pigmentation and preventive conservation of cultural and historically relevant mural painting through FEDER–Operational Program for Competitiveness and Internationalization [Grant Number POCI-01–0145-FEDER-029157] and National Funds from FCT–Foundation for Science and Technology [Grant Number PTDC/HAR-ARQ/29157/2017]; Alexandra Marco PhD research supported by Foundation for Science and Technology (FCT) through POCH–Operational Human Capital Program, co-participated by the Social European Fund (FSE) and MCTES National Fund [Grant Number SFRH/BD/125596/2016]; and FCT through the Strategic Projects CITAR (UID/EAT/0622/2016) and CBQF [Grant Number UID/Multi/50016/2013]. Dr. David M. Freire-Lista is supported by FCT through Stimulus of Scientific Employment, Individual Support 2017 [Grant Number CEECIND/03568/2017].

El proyecto supone un trabajo de laboratorio de síntesis química orgánica e inorgánica, con manejo de distintas técnicas instrumentales (en algunos casos por parte del alumno), y posterior interpretación de los datos analíticos y espectroscópicos. Tras una revisión bibliográfica, el alumno preparará complejos de paladio hidrosolubles y realizará un estudio preliminar de sus aplicaciones en distintos campos. En este caso se plantea si es posible sintetitar tetrakis sacarinato complejos similares a otros descritos en la bibliografía con ligandos análogos como 1Me.uracilo y ftalimida, que han presentado estructuras singulares y potenciales aplicaciones catalíticas. Escuela Técnica Superior de Ingeniería Industrial Universidad Politécnica de Cartagena

The main part of this thesis focuses on the production and characterisation of carbon nanodots. Regarding the production methods of the CNDs chosen in this work, CNDs produced by two clearly different bottom-up methods have been studied in detail. On the one hand, the solvothermal method has been used. This method consists of heating a liquid, in a closed container, above its boiling point, generating a pressure higher than atmospheric pressure, and thus inducing the condensation of CNDs. The obvious advantages of this synthetic method are: it is easy, cheap and environmentally friendly (provided that the solvent used in the solvothermal method is an environmentally friendly solvent, in our case we used water and ethanol). All these advantages provided a great opportunity to easily prepare and investigate CNDs, which, when prepared by this method, were found to have promising properties such as solubility in aqueous media, biocompatibility, photocatalytic activity in heterostructures with TiO2 and biocidal properties that can be employed to prepare biocidal polymer surfaces. The combination of the advantages proposed by the synthetic method and the promising properties of the products obtained have made this method the most common synthetic procedure for the production of CNDs...

Low-valent group 15 compounds stabilized by pincer ligands have gained particular interest, given their direct access to fine-tune their reactivity by the coordination pattern. Recently, bismuth has been employed in a variety of catalytic transformations by taking advantage of the (+1/+3) redox couple. In this work, we present a detailed quantum–chemical study on the electronic structure of bismuth pincer complexes from two different families, namely, bis(ketimine)phenyl (NCN) and triamide bismuthinidene (NNN). The use of the so-called effective oxidation state analysis allows the unambiguous assignation of the bismuth oxidation state. In contrast to previous studies, our calculations suggest a Bi(+1) assignation for NCN pincer ligands, while Bi(+3) character is found for NNN pincer complexes. Notably, regardless of its oxidation state, the central bismuth atom disposes of up to two lone pairs for coordinating Lewis acids, as indicated by very high first and second proton affinity values. Besides, the Bi–NNN systems can also accommodate two Lewis base ligands, indicating also ambiphilic behavior. The effective fragment orbital analysis of Bi and the ligand allows monitoring of the intricate electron flow of these processes, revealing the noninnocent nature of the NNN ligand, in contrast with the NCN one. By the dissection of the electron density into effective fragment orbitals, we are able to quantify and rationalize the Lewis base/acid character., Effective oxidation state analysis sheds light on the electronic structure of chemical systems. The oxidation state of bismuthinidene pincer complexes can be assigned as Bi(+1) or Bi(+3) depending on the nature of the ligands. Despite this assignation, the reactivity pattern as Lewis base or acid is similar. The occupation of the effective fragment orbitals gives a straightforward method to quantify the reactivity.

17 p.-8 fig., SARS-CoV-2 vaccines currently in use have contributed to controlling the COVID-19 pandemic. Notwithstanding, the high mutation rate, fundamentally in the spike glycoprotein (S), is causing the emergence of new variants. Solely utilizing this antigen is a drawback that may reduce the efficacy of these vaccines. Herein we present a DNA vaccine candidate that contains the genes encoding the S and the nucleocapsid (N) proteins implemented into the non-replicative mammalian expression plasmid vector, pPAL. This plasmid lacks antibiotic resistance genes and contains an alternative selectable marker for production. The S gene sequence was modified to avoid furin cleavage (Sfs). Potent humoral and cellular immune responses were observed in C57BL/6J mice vaccinated with pPAL-Sfs + pPAL-N following a prime/boost regimen by the intramuscular route applying in vivo electroporation. The immunogen fully protected K18-hACE2 mice against a lethal dose (105 PFU) of SARS-CoV-2. Viral replication was completely controlled in the lungs, brain, and heart of vaccinated mice. Therefore, pPAL-Sfs + pPAL-N is a promising DNA vaccine candidate for protection from COVID-19., This work was funded by PTI-Salud Global (CSIC), Center for Technological and Industrial Development (CDTI), REACT-ANTICIPA-UCM (Comunidad de Madrid), and European Research Council (Advanced Grant VERDI, ERC2015AdG grant number 694160).

Polymers are extensively used in food and beverage packaging to shield against contaminants and external damage due to their barrier properties, protecting the goods inside and reducing waste. However, current trends in polymers for food, water, and beverage applications are moving forward into the design and preparation of advanced polymers, which can act as active packaging, bearing active ingredients in their formulation, or controlling the head-space composition to extend the shelf-life of the goods inside. In addition, polymers can serve as sensory polymers to detect and indicate the presence of target species, including contaminants of food quality indicators, or even to remove or separate target species for later quantification. Polymers are nowadays essential materials for both food safety and the extension of food shelf-life, which are key goals of the food industry, and the irruption of smart materials is opening new opportunities for going even further in these goals. This review describes the state of the art following the last 10 years of research within the field of food and beverage polymer's applications, covering present applications, perspectives, and concerns related to waste generation and the circular economy.

[EN] The excellent high-durability features of ultra-high performance fibre-reinforced concrete (UHPFRC) have been verified in laboratory studies, but its performance under service conditions are being studied. Indeed, structural health monitoring (SHM) can be considered an efficient strategy to assess built structures in which concrete matrix performance differs from that those found when assessing laboratory samples (variable actions, cracking, etc.). This work presents INESSCOM, an automated corrosion rate monitoring system, as an innovative support to SHM strategy to monitor UHPFRC structures in terms of durability. Its innovation lies in its durable and multi-parametric sensor designed to be embedded in multiple parts of a structure. The results from pre-vious laboratory tests and those obtained during real-time monitoring of an offshore UHPFRC raft are presented. Acceptable deviation of 20% was obtained in corrosion rate measurements with the advantageous reference-electrode-free cell of the sensor with respect to the classical three-electrode cell. Furthermore, sensor provided accurate corrosion measurements in UHPFRC despite its extremely high electrical resistivity and large amount of steel fibres. After 17-month monitoring of the UHPFRC raft, excellent perfor-mance was evidenced under service conditions with corrosion rate values always, UPV, Grant/Award Number: SP20180245; Spanish Ministry of Economy and Competitiveness, Grant/Award Numbers: BIA2016-78460-C3-3-R, PID2020-119744RB-C21, PID2020-119744RB-C22; Spanish Ministry of Science and Innovation, Grant/Award Number: FPU13/00911

Osteomyelitis is a hard-to-treat infection of the bone and bone marrow that is mainly caused by Staphylococcus aureus, with an increasing incidence of methicillin-resistant S. aureus (MRSA). Owing to the aggressiveness of these bacteria in colonizing and destroying the bone, systemic antibiotic treatments fail to eradicate the infection. Instead, it normally entails surgery to remove the dead or infected bone. In this work, we report bone-targeted mesoporous silica nanoparticles for the treatment of osteomyelitis. The nanoparticles have been engineered with a functional gelatine/colistin coating able to hamper premature release from the mesopores while effectively disaggregating the bacterial biofilm. Because antibiotic resistance is a global emergency, we have designed two sets of identical nanoparticles, carrying each of them a clinically relevant antibiotic, that have demonstrated to have synergistic effect. The bone-targeted nanoparticles have been thoroughly evaluated in vitro and in vivo, obtaining a notable reduction of the amount of bacteria in the bone in just 24 h after only one dose, and paving the way for localized, nanoparticle-mediated treatment of MRSA-caused osteomyelitis. Statement of significance In this work, we propose the use of bone-targeted mesoporous silica nanoparticles to address S. aureus-caused osteomyelitis that render synergistic therapeutic effect via multidrug delivery. Because the bacterial biofilm is responsible for an aggressive surgical approach and prolonged antibiotic treatment, the nanoparticles have been functionalized with a functional coating able to both disaggregate the biofilm, hamper premature antibiotic release and protect the intact bone. These engineered nanoparticles are able to effectively target bone tissue both in vitro and in vivo, showing high biocompatibility and elevated antibacterial effect.

[ES] Esta tesis doctoral titulada "Evaluación preclínica de estrategias basadas en la senescencia para mejorar la terapia contra el cáncer" se centra en explotar la senescencia como opción terapéutica en los tratamientos contra el cáncer mediante el diseño, la síntesis y la evaluación in vitro e in vivo de varios nanodispositivos y profármacos, así como la identificación de un nuevo fármaco senolítico. En el primer capítulo experimental evaluamos el efecto negativo de la senescencia endotelial en el contexto tumoral y la consecuencia de su eliminación mediante el uso del senolítico navitoclax. Comprobamos que el tratamiento sistémico con palbociclib en un modelo ortotópico de cáncer de mama en ratones induce senescencia en las células endoteliales vasculares, generando un endotelio alterado funcionalmente que favorece la migración de células cancerosas. La recuperación de la funcionalidad endotelial se consigue con una estrategia terapéutica que, tras la inducción de senescencia con palbociclib, elimina las células senescentes (senólisis) con la nanopartícula (NP(nav)-Gal). En el modelo preclínico, el tratamiento combinado de palbociclib con NP(nav)-Gal disminuyó la senescencia endotelial en venas, así como los nódulos metastásicos en los pulmones. Teniendo en cuenta los resultados obtenidos, el capítulo dos se describe una estrategia terapéutica en dos pasos similar a la anterior para cáncer de mama triple negativo. En este caso se emplea un modelo de ratón implantado con xenoinjertos humanos de este tipo de cáncer para evaluar el efecto de la terapia combinada de palbociclib y navitoclax. Para superar los efectos secundarios del tratamiento con navitoclax (principalmente trombocitopenia), evaluamos el efecto del profármaco nav-Gal. La senescencia inducida por la terapia con palbociclib, seguida de una terapia adyuvante con navitoclax o nav-Gal, provoca la eliminación sinérgica de las células senescentes tumorales y la reducción del crecimiento tumoral y de la metástasis pulmonar en el modelo utilizado de ratones con xenoinjertos de cáncer de mama humano agresivo. El capítulo tres se centra en el diseño y el desarrollo de un nuevo sistema de comunicación de nanopartículas por estigmergía para mejorar la terapia tumoral en el cáncer de mama. La comunicación de nanopartículas por estigmergía consiste en un sistema secuencial de dos nanopartículas en la que la primera modifica el entorno permitiendo que la segunda nanopartícula pueda actuar. Para ello, nos basamos de nuevo en una terapia en dos pasos, siendo el primer paso la inducción de senescencia con palbociclib en las células tumores y el segundo su posterior eliminación con navitoclax. Con este objetivo, se prepararon dos nanodispositivos: el primer nanodispositivo (NP(palbo)PEG-MUC1) se cargó con palbociclib y se funcionalizó con un aptámero dirigido a la proteína de superficie MUC1, frecuentemente sobreexpresada en las células tumorales de mama; para el segundo nanodispositivo se empleó la nanopartícula senolítica NP(nav)-Gal. Cuando ambas nanopartículas se administraron secuencialmente se consiguió un efecto aumentado, retrasando el crecimiento tumoral y reduciendo las metástasis en pulmón en el modelo descrito previamente de ratones con xenoinjerto hTNBC. En el último capítulo identificamos un nuevo agente senolítico (H14) que puede eliminar a las células tumorales senescentes de melanoma con una eficacia y seguridad óptima in vivo. Para ello, se realizó un cribado de una biblioteca combinatoria de hexapéptidos de D-aminoácidos en células senescentes de melanoma SK-Mel-103, en las que la inducción de la senescencia se había producido mediante el tratamiento con palbociclib. El tratamiento combinado de palbociclib y el hexapéptido H14 logró una mejora en la eliminación de células tumorales senescentes in vivo, así como en la reducción del crecimiento tumoral, alcanzando efectos similares al tratamiento combinado de palbociclib con navitoclax., [CA] Aquesta tesi doctoral titulada "Avaluació preclínica d'estratègies basades en la senescència per millorar la teràpia contra el càncer" se centra a explotar la senescència com a opció terapèutica en els tractaments contra el càncer mitjançant el disseny, la síntesi i l'avaluació in vitro i in vivo diversos nanodispositius i profàrmacs, així com la identificació d'un nou fàrmac senolític. Al primer capítol experimental avaluem l'efecte negatiu de la senescència endotelial en el context tumoral i la conseqüència de la seva eliminació mitjançant l'ús del senolític navitoclax. Comprovem que el tractament sistèmic amb palbociclib en un model ortotòpic de càncer de mama en ratolins indueix senescència a les cèl·lules endotelials vasculars, generant un endoteli alterat funcionalment que afavoreix la migració de cèl·lules canceroses. La recuperació de la funcionalitat endotelial s'aconsegueix amb una estratègia terapèutica que, després de la inducció de senescència amb palbociclib, elimina les cèl·lules senescents (senòlisi) amb la nanopartícula (NP(nav)-Gal). En el model preclínic, el tractament combinat de palbociclib amb NP(nav)-Gal va disminuir la senescència endotelial en venes, així com els nòduls metastàsics als pulmons. Tenint en compte els resultats obtinguts, el capítol dos es descriu una estratègia terapèutica en dos passos similar a l'anterior per al càncer de mama triple negatiu. En aquest cas es fa servir un model de ratolí implantat amb xenoempelts humans d'aquest tipus de càncer per avaluar l'efecte de la teràpia combinada de palbociclib i navitoclax. Per superar els efectes secundaris del tractament amb navitoclax (principalment trombocitopènia), avaluem l'efecte del profàrmac nav-Gal. La senescència induïda per la teràpia amb palbociclib, seguida d'una teràpia adjuvant amb navitoclax o nav-Gal, provoca l'eliminació sinèrgica de les cèl·lules senescents tumorals i la reducció del creixement tumoral i de la metàstasi pulmonar en el model utilitzat de ratolins amb xenoempelts de càncer de mama humà agressiu. El capítol tres se centra en el disseny i desenvolupament d'un nou sistema de comunicació de nanopartícules per estigmergia per millorar la teràpia tumoral al càncer de mama. La comunicació de nanopartícules per estigmergia consisteix en un sistema seqüencial de dues nanopartícules on la primera modifica l'entorn permetent que la segona nanopartícula pugui actuar. Per això, ens basem de nou en una teràpia en dos passos, sent el primer pas la inducció de senescència amb palbociclib a les cèl·lules tumors i el segon la posterior eliminació amb navitoclax. Amb aquest objectiu, es van preparar dos nanodispositius: el primer nanodispositiu (NP(palbo)PEG-MUC1) es va carregar amb palbociclib i es va funcionalitzar amb un aptàmer dirigit a la proteïna de superfície MUC1, freqüentment sobreexpressada a les cèl·lules tumorals de mama; per al segon nanodispositiu es va emprar la nanopartícula senolítica NP(nav)-Gal. Quan ambdues nanopartícules es van administrar seqüencialment es va aconseguir un efecte augmentat, endarrerint el creixement tumoral i reduint les metàstasis en pulmó en el model descrit prèviament de ratolins amb xenoempelt hTNBC. A l'últim capítol identifiquem un nou agent senolític (H14) que pot eliminar les cèl·lules tumorals senescents de melanoma amb una eficàcia i seguretat òptima in vivo. Per fer-ho, es va realitzar un cribratge d'una biblioteca combinatòria d'hexapèptids de D-aminoàcids en cèl·lules senescents de melanoma SK-Mel-103, on la inducció de la senescència s'havia produït mitjançant el tractament amb palbociclib. El tractament combinat de palbociclib i l'hexapèptid H14 va aconseguir una millora en l'eliminació de cèl·lules tumorals senescents in vivo, així com en la reducció del creixement tumoral, aconseguint efectes similars al tractament combinat de palbociclib amb navitoclax., [EN] This PhD thesis entitled "Preclinical evaluation of senescence-based strategies to improve cancer therapy" focuses on exploiting senescence as a therapeutic option in cancer treatments through design, synthesis and in vitro and in vivo evaluation. of several nanodevices and prodrugs, as well as the identification of a new senolytic drug. In the first experimental chapter we evaluated the negative effect of endothelial senescence in the tumor context and the consequence of its elimination through the use of the senolytic navitoclax. We found that systemic treatment with palbociclib in an orthotopic model of breast cancer in mice induces senescence in vascular endothelial cells, generating a altered endothelium that favors the migration of cancer cells. Recovery of endothelial functionality was achieved, after palbociclib-senescence induction, by removal of senescent cells (senolysis) with navitoclax-loaded nanoparticles (NP(nav)-Gal). In a preclinical model, the combined treatment of palbociclib with NP(nav)-Gal decreased endothelial senescence in veins as well as in metastatic nodules in the lungs. Taking into account the results obtained, chapter two describes a similar therapeutic strategy for triple-negative breast cancer. In this case, a human xenograft mice model was employed to evaluate the effect of combined therapy of palbociclib plus navitoclax. To overcome the side effects of navitoclax treatment (mainly thrombocytopenia), we evaluated the effect of the prodrug nav-Gal. Palbociclib therapy-induced senescence, followed by adjuvant navitoclax or nav-Gal therapy, resulted in synergistic clearance of senescent tumor cells and reduction of tumor growth and lung metastasis in the xenograft mice model of aggressive human TNBC. Chapter three focuses on the design and development of a new stigmergy nanoparticle communication system to improve tumor therapy in breast cancer. The communication of nanoparticles by stigmergy consists of a sequential system of two nanoparticles in which the first modifies the environment allowing the second nanoparticle to act. To do this, we again rely on a two-step therapy, the first step being the induction of senescence with palbociclib in tumor cells and the second its subsequent elimination with navitoclax. To this end, two nanodevices were prepared: the first nanodevice (NP(palbo)PEG-MUC1) was loaded with palbociclib and functionalized with an aptamer targeting the surface protein MUC1, frequently overexpressed in breast tumor cells; for the second nanodevice, the senolytic nanoparticle NP(nav)-Gal was used. When both nanoparticles were administered sequentially, an increased effect was achieved, delaying tumor growth and reducing lung metastases in the previously described model of hTNBC xenograft mice. In the last chapter we identified a new senolytic agent (H14) that can kill senescent melanoma tumor cells with optimal efficacy and safety in vivo. For this, a combinatorial library of D-amino acid hexapeptides was screened in senescent SK-Mel-103 melanoma cells, in which senescence induction had occurred by treatment with palbociclib. The combined treatment of palbociclib and H14 hexapeptide achieved an improvement in the elimination of senescent tumor cells in vivo, as well as in the reduction of tumor growth, reaching similar effects to the combined treatment of palbociclib and navitoclax. Future breakthroughs in the field of cellular senescence treatment are expected. We hope that the results achieved in this PhD thesis will open new research opportunities and inspire the development of advanced strategies with smart nanodevices and prodrugs for their application in the field of cellular senescence and other different biomedical areas and in sensing and communication technologies to solve patient needs.

[ES] Este proyecto se basa en la síntesis y caracterización de nanopartículas (NP) con propiedades antimicrobianas. Las NP se prepararán a partir de sílice porosa (MCM-41) con una elevada porosidad capaz de encapsular sustancias o fármacos de interés, en nuestro caso líquidos iónicos (RTIL). La liberación de RTIL tiene efectos terapéuticos ya que potencia un ambiente antimicrobiano. Se ha establecido que el mecanismo de muerte celular se basa en la alteración de la osmolaridad del medio, por la que se produce un flujo libre de electrolitos fuera del microbio provocando su muerte. Para garantizar la liberación controlada y específica de RTIL, estos se encapsulan en los poros de las NP y quedan atrapados en su interior empleando puertas moleculares. Como puertas moleculares se emplearán biomoléculas como polisacáridos o péptidos que se van a degradar específicamente solo en presencia de enzimas secretadas por las bacterias diana produciendo la liberación de RTIL y la muerte de los microbios. En el proyecto se caracterizarán todos los sólidos mediante difracción de rayos X (DRX), dispersión de luz dinámica (DLS), potencial Z, porosimetría, etc. Se medirán las propiedades de liberación de los nanomateriales en condiciones de laboratorio y se realizarán experimentos en cultivos bacterianos para cuantificar sus efectos antimicrobianos y su posible potencial terapéutico frente infecciones microbianas., [EN] This project is based on the synthesis and characterization of nanoparticles (NPs) with antimicrobial properties. The NPs will be prepared from porous silica (MCM-41) with a high porosity capable of encapsulating substances or drugs of interest, in our case ionic liquids (RTIL). RTIL release has therapeutic effects as it enhances an antimicrobial environment. It has been established that the mechanism of cell death is based on the alteration of the osmolarity of the medium, whereby a free flow of electrolytes out of the microbe causing its death. To ensure the controlled and specific release of RTILs, they are encapsulated in the pores of the NPs and trapped inside using molecular gates. Biomolecules, such as polysaccharides and peptides, will be used as molecular gates. These molecular gates will be specifically hydrolysed only in the presence of enzymes secreted by the target bacteria leading to RTIL release and microbial killing. In the project all solids will be characterized by X-ray diffraction (XRD), dynamic light scattering (DLS), Z-potential, porosimetry, etc. The release properties of the nanomaterials will be measured under laboratory conditions and experiments will be performed on bacterial cultures to quantify their antimicrobial effects and their possible therapeutic potential against microbial infections.

[EN] Potential step voltammetry (PSV) was introduced in earlier works as an advantageous alternative to traditional methods for measuring corrosion rate in reinforced concrete. The present study aims to improve PSV to maximize its applicability in corrosion rate monitoring, that is, beyond the narrowly-defined steel¿concrete systems in which was initially validated. It was therefore identified necessary to address the most suitable PSV pulse amplitudes to accurately obtain the Tafel lines and, therefore, corrosion rate in steel-mortar systems with well-differentiated ohmic drop. PSV findings were compared to reference methods, i.e. Tafel intersection and linear polarization resistance. As a novelty, we propose a procedure to improve the reliability of the PSV-determined Tafel lines, which is based on three protocols (P1, P2 and P3). P1 consists of a specific pulse sequence to accurately characterize the morphology of the polarization curve without disturbing the system. P2 consists of two short pulses for determining the ohmic drop compensation factor. Finally, P3 consists of a simple calculation procedure to accurately adjust the PSV pulse amplitudes (V) to the steel¿concrete system assessed, thus obviating the need for preset values and, therefore, ensuring accurate corrosion rate results. The procedure proposed is intended to improve PSV with a view to its consolidation as a reliable tool for the unsupervised monitoring of real structures., Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work was supported by the pre-doctoral scholarship granted to Jose Enrique Ramon Zamora by the Spanish Ministry of Science and Innovation (Grant Number FPU13/00911). We would also like to acknowledge financial support from the Spanish Ministry of Science and Innovation through the national programs of oriented research, development and innovation to societal challenges (Project Numbers BIA2016-78460-C33-R, PID2020-119744RB-C21 and PID2020-119744RB-C22). To the Universitat Politecnica de Valencia for the financial support in the project "Ayudas a Primeros Proyectos de Investigacion (PAID-0618)"-SP20180245.

212 p. Thesis Abstract Organic-inorganic halide perovskite solar cells(PSCs) have emerged as one of the best candidates in next generation photovoltaics since their introduction in 2009. The power conversion efficiency (PCE) has dramatically increased from 3.8% to 25.7% in a decade. However, due to their limited device stability, the path to commercialization has been hindered, despite excellent PCEs. The highest performing PSCs is composed of several layers such as electron transport layers, an n-type mesoporous TiO2 layer, a perovskite layer, a hole transporting layer and a metal electrode. The high PCE can be achieved by effectively extracting and collecting the photo generated holes and selectively reducing the charge recombination loss. The state-of-art Spiro-OMeTAD is themost commonly used hole transporting material in the literature,however, its high cost due to multistep synthesis process, complex purification and instability caused by adding of hygroscopic p-typedopants, hinders the large-scale industrialization of PSCs. Thus, thedevelopment of new designed HTMs is highly desired.Additionally, the dimensionality of the perovskite influences the performance and stability of the PSCs. The reduction of dimensionality to produce lower-dimensional perovskites or analternative approach to implement an interfacial layer of the least amount of large organic cation to 3D perovskite surface to form bilayer or layered/3D mixed dimensional perovskites greatlyenhance the photovoltaic performance and stability of PSCs.Thus, the studies in this thesis aim to develop new hole-transporting materials that would be inexpensive and easily synthesizable andcan be effectively implemented for PSC applications. A series ofHTMs based on small molecules were designed and synthesized and investigated to understand the behaviour as a charge selective layerin PSCs, to further reduce the cost and improve the stability.Further more, the thesis discusses the work on the dimensionality of the perovskite and interface engineering of the perovskite absorber layer with large organic cations for improved performance and longterm stability purposes.Thus, the thesis aims to discuss the studies and investigations on themolecularly designed hole-transporting materials (HTMs) andemploy the large-size organic cation as an interface layer or dopingto form reduced mixed-dimensional perovskite absorber forenhancing the overall performance and long-term stability of thePSCs. Bcmaterials: Basque Center for Materials, applications & nanostructures