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[eng] This doctoral work investigates nucleic acids' thermodynamic and kinetic properties. The main objective is the characterization of the energetics and the folding mechanisms driving the hybridization of DNA and RNA molecules. A rigorous study of these processes is key to understanding the diversity of behaviors observed for nucleic acids and predicting their main features. The thesis is organized into four main parts. In Part I, we overview single-molecule force spectroscopy and some of the most common and relevant experimental techniques (Chapter 2). Among these, we describe optical trapping with laser optical tweezers, the experimental method used to carry out this work. The experimental setup is also accurately described (Chapter 3). Then, we discuss the biological concepts and the statistical tools used in the thesis. This includes fluctuation relations (Chapter 4), nucleic acids structure, thermodynamic modeling of the unzipping experiments (Chapter 5), and the transition state theory for two-state systems in thermodynamic equilibrium (Chapter 6). In Part II, we report the results of calorimetry force spectroscopy experiments on long DNA hairpins. We studied the temperature dependence of free energy, entropy, and enthalpy by carrying out unzipping experiments in the temperature range of 7 – 42°C. Even though the effects of temperature are known to be non-negligible, an accurate characterization of the thermodynamics parameters at the single base pair level still needs to be improved. Therefore, we developed a powerful method to accurately assess the temperature dependence of the entropy and enthalpy parameters, ultimately permitting us to measure the specific heat change per base pair. In Part III, we report the study of the energetics and kinetics of RNA folding, focusing on the complex mechanisms underlying RNA hybridization. By mechanically unzipping a long RNA hairpin, we derived the ten nearest-neighbor base pair RNA free energies in sodium and magnesium (Chapter 8). To characterize the irreversibility of the unzipping–rezipping process and the folding dynamics, we hypothesize that stem-loops structures forming along the unpaired RNA strands drive the folding (Chapter 9). This phenomenon is modeled by introducing a barrier energy landscape of the stem-loop structures forming along the complementary strands, which compete against the formation of the native hairpin. Finally, in Part IV, the results of pulling experiments of short RNA hairpins at low temperatures are reported. After reaching 5 – 7°C, short RNA sequences designed to fold as simple duplexes exhibit misfolded states competing with the native fold. Despite different sequences forming different misfolded structures, all of them share common features: they are very compact and brittle, and their stability does not depend on the presence of monovalent or divalent ions. RNA cold misfolding appears to be a general phenomenon questioning our understanding of RNA folding., [spa] En este trabajo doctoral se han investigado las propiedades termodinámicas y cinéticas de los ácidos nucleicos. El principal objetivo era el estudio de los mecanismos de plegamiento que se llevan a cabo en la hibridación de moléculas de ADN y ARN y su caracterización energética. La tesis está organizada en cuatro partes principales. En la Parte I, repasamos la espectroscopia de fuerza de molécula única y algunas de las técnicas experimentales más relevantes en el estudio del plegamiento de ácidos nucleicos (Capítulo 2), enfocándose en las pinzas ópticas (método experimental utilizado en esta tesis) (Capítulo 3). Además, se introducen los conceptos biológicos y las herramientas estadísticas utilizadas en la tesis, incluyendo los teoremas de fluctuación (Capítulo 4), la estructura de ácidos nucleicos, el modelo termodinámico de los experimentos de desplegamiento mecánico (Capítulo 5) y la teoría de los estados de transición (Capítulo 6). En la Parte II, reportamos los resultados de experimentos de calorimetría con pinzas ópticas sobre horquillas largas de ADN en un rango de temperaturas de 7 – 42 °C. Se ha estudiado la dependencia con la temperatura de la energía libre, la entropía y la entalpía. Hemos desarrollado un metodología para evaluar con precisión la dependencia de la temperatura de la entropía y entalpía, y finalmente medir el cambio del calor específico nivel de par de bases individuales. La Parte III, describe el estudio termodinámico y cinético del plegamiento del ARN, centrándonos en los mecanismos complejos que subyacen en su hibridación. Desplegando mecánicamente una horquilla larga de ARN, derivamos los diez parámetros de energías libres de ARN en sodio y magnesio (Capítulo 8). Para caracterizar la irreversibilidad del proceso de desplegamiento-plegamiento y su dinámica, planteamos la hipótesis de que la formación de “bucles en las hebras” desapareadas (stem-loops) de ARN impulse la formación de la horquilla (Capítulo 9). Este fenómeno se modela mediante la introducción de un paisaje de energía de los stem-loops que se forman a lo largo de las hebras complementarias, compitiendo contra la formación de la horquilla nativa. Finalmente, en la Parte IV, se reportan los resultados experimentales de desplegamiento de moléculas cortas de ARN a bajas temperaturas. Entre 5 y 7 °C, diferentes secuencias cortas de ARN diseñadas para plegarse en horquillas simples exhiben estados mal plegados que compiten con el estado nativo. Todas las secuencias estudiadas comparten características comunes: son compactas y frágiles, y su estabilidad no depende de la presencia de iones mono o divalentes. El mal plegamiento en frío del ARN parece ser un fenómeno general que cuestiona nuestra comprensión del plegamiento del ARN.

188 p. En la presente tesis se estudian mediante métodos experimentales (espectroscopia Raman, espectroscopia de impedancia electroquímica y difracción de rayos X) y teóricos (cálculos de primeros principios) la formación, estructura y conductividad protónica de clatratos de agua encapsulando ácidos. En particular,presentamos un estudio teórico mediante cálculos ab initio basados en la teoría del funcional de la densidad del hidrato de HPF6 en la estructura SVII y de la estabilidad de moléculas de H3PO4, H2PO2F2 yH3PO3F como impurezas sustitucionales en dicha estructura. Nuestros cálculos confirman que la estructura es más estable cuando dichos dopantes sustituyen a aniones de PF6-, al menos a bajas concentraciones. Este resultado es consistente con resultados experimentales de la literatura y confirma la importancia del papel de las impurezas en la estabilidad y las propiedades del hidrato de HPF6. Por otro lado, nuestros resultados experimentales se centran en los hidratos mixtos de tetrahidrofurano (THF) yHClO4 para distintas fracciones HClO4/THF. Para dichos sistemas hemos realizado medidas de difracción de rayos, espectroscopia e imagen Raman, y medidas de impedancia electroquímica. De esta manera hemos podido correlacionar los cambios estructurales y de conductividad observados con el número de hidratación y la fracción ácida. A partir de estos datos se han generado modelos para entender la conductividad que ponen de relieve la importancia de la estructura y organización del sistema en la escala meso/macroscópica.

180 p. The theory describing the interaction between light and matter at nanoscale is nearly as old as quantum mechanics. Over the years, it has been shown that such theoretical models not only enable materials scientists to deepen their physical understanding of the underlying microscopic mechanisms but also provide the possibility to develop novel materials and devise advanced mechanisms to use within emerging technological applications. With the steady increase in computational power, the combination of experiments with theoretical and computational modeling is currently perceived as a promising approach to significantly reduce the time and effort to optimize the functionality of a material for a given application. This usually involves simulating materials at different scales, making use of the so-called ab initio electronic structure methods to describe the behavior of materials at the atomic scale. In this thesis, we particularly focus on the ab initio many-body perturbation theory (MBPT) providing powerful tools to describe the electronic excitations of materials. Within the MBPT, the GW approximation is a Green's function-based framework which is extensively employed to investigate the electronic structure of diverse materials in both finite and extended phases at the same level of reasonable accuracy. However, the computational complexity associated with the canonical implementation of the method often hinders its application in large systems with more than a hundred atoms. In the present dissertation, after introducing the underlying methodology, we discuss a new implementation of the one-shot GW wherein the computation of the quasiparticle energies requires neither the explicit calculation of the response function nor the inversion of dielectric matrices. In doing so, we ultimately benefit from the sparsity associated with the use of a basis set of atomic orbital, and design iterative algorithms dealing with matrix-vector products instead of memory-demanding matrix-matrix operations. To validate our numerical implementation, we rigorously test the performance of the iterative algorithm for a variety of small molecules and a few relatively large systems, such as buckyball fullerenes with up to 320 atoms. By inspecting the memory usage of the proposed algorithms, we demonstrate the capability of the iterative implementation to treat large systems with limited computational resources.In the present doctoral thesis, we also discuss the application of MBPT methods to molecular systems. In the realm of MBPT, the GW method is the predominant framework to describe the spectra of single-particle-like electronic excitations (quasiparticles). To demonstrate this point, we benchmark the ionization energies, as a fundamental key quantity for many optoelectronic applications, of 42 open-shell molecules computed with the G0W0 method using different unrestricted stating-point calculations. Although the final results point to an undesired dependency on the choice of the initial mean-field solutions, the average performance of the G0W0 correction on top of standard hybrid functionals is found reasonably accurate as compared to the results obtained from the high-level quantum chemistry methods. The significant role of correlation effects captured by the GW self-energy is also stressed in the case of a few examples for which the mean-field methods provide a qualitatively incorrect estimation of the molecular orbital ordering.Extending our study to solid state, we investigate the electronic structure and optical properties of a few organic semiconductors by a combination of MBPT methods. For the diindenoperylene (DIP) molecular crystal, we show that the quasiparticle band structure as calculated within the GW approximation results in a transport gap in excellent agreement with photo-emission spectroscopy data, while the absorption spectra and optical gap predicted by solving Bethe-Salpeter equation reconcile available experimental data. Here, we also explore the p-type doping of the DIP crystal with two recently proposed electron-accepting molecular dopants, and characterize the optical and electronic properties of the doped DIP crystals using the same methodology. As compared to pristine DIP, we find that the band gap of both doped crystals is narrowed considerably due to the formation of hybridized states at the valence band-edge associated with a host-dopant charge-transfer complex. These hybridized electronic structure of the doped DIP crystals results in a broad absorption spectrum associated with new optically active excitations spanning over infrared and visible ranges. While the strong transitions in the infrared range are attributed to the excitations with a noticeable charge-transfer character, we show that the absorption spectra of both doped DIP crystals features an onset which is considerably lower than that of the pristine DIP absorption. Therefore, the two proposed doped crystals appear as technologically relevant materials for optoelectronic applications. DIPC:Donostia International Physics Center CFM: Centro de Física de Materiales

346 p. (eng.) 246 p. (eusk.) En esta tesis se desarrollan y estudian materiales híbridos zeotípicos fotoactivos para la obtención de sistemas multifuncionales en estado sólido con interesantes propiedades ópticas aptas para aplicaciones en el campo de la fotónica. Para ello, se atrapan colorantes orgánicos en nanocavidades restringidas de estructuras inorgánicas de aluminofosfato dopadas con metales (con Si o Mg, obteniendo estructuras tipo SAPO y MgAPO, respectivamente) para promover procesos fotofísicos nuevos y/o mejorados en los materiales por efecto sinérgico, en comparación con los fluoróforos aislados.En este trabajo se preparan un gran número de materiales de colorante-AlPO, combinando varias estructuras con diferentes formas y tamaños de poros/canales en el rango de dimensiones moleculares, con una amplia gama de colorantes orgánicos, principalmente de las familias de estirilos y aromáticos fusionados de tres anillos. La inclusión de fluoróforos en las cavidades de los AlPOs realizada "in situ" por el método de inclusión por cristalización permite el desarrollo directo de materiales híbridos fluorescentes con funcionalidades ópticas destacadas y específicas en un solo paso y en cortos periodos de tiempo, describiendo así una síntesis rentable y eficiente para sistemas avanzados.Por un lado, como resultado de la sinergia entre moléculas fotoactivas push-pull con anfitriones de aluminofosfato canalizados en 1D (AFI, ATS y AEL) y una estructura de tipo jaula-3D (CHA), se obtienen sistemas sólidos ópticamente densos con capacidad de fluorescencia mejorada y respuesta altamente anisotrópica a la luz linealmente polarizada. A través de esta estrategia las aplicaciones logradas son diversas, desde emisores NIR hasta generadores de segundo armónico y láseres en estado sólido a nivel de partícula.Por otro lado, la oclusión simultánea de diferentes especies fotoactivas en los aluminofosfatos (IFO y AEL) promueve la probabilidad de procesos de FRET en cascada entre moléculas orgánicas ocluidas en el espacio restringido de los canales zeotípicos. La coencapsulación de especies adecuadas y racionalmente seleccionadas (pares FRET) proporciones idóneas conduce a nuevos sistemas de antenas artificiales, con propiedades como la emisión sintonizable y la emisión de luz blanca.A lo largo de este trabajo, las síntesis de los materiales híbridos dopados con colorantes se optimizan (variando la composición del gel, la temperatura y el tiempo y método de calentamiento) y la morfología y cristalización de todas las fases presentadas se comprueban mediante técnicas de SEM y difracción de rayos-X en polvo. Las propiedades fotofísicas de los materiales híbridos y de los colorantes fotoactivos se analizan en profundidad mediante técnicas de estado estacionario y resueltas en el tiempo (espectroscopias de absorción y emisión), así como mediante microscopía de fluorescencia, que permite el análisis a nivel de partícula. Además, se demuestra la aplicabilidad final de los materiales mediante técnicas sofisticadas como la detección de señales de generación de segundos armónicos y la respuesta de acción del microláser

Producción Científica, The rotational spectrum (4–40 GHz and 50–330 GHz) has been measured and analyzed for trifluoroacetaldehyde, also known as fluoral (CF3CHO), which is one of the degradation products of the fluorinated contaminants emitted into the atmosphere. The complexity of the spectroscopic analysis of this molecule arises from the strong coupling between the internal rotation motion of CF3 group and the overall rotation of the molecule. The value obtained for its coupling constant (ρ = 0.91723481(49)) is comparable to the corresponding value of methanol (CH3OH, ρ = 0.81), which is known for its complex spectrum. A total of 12,322 transitions of the ground, the first and second excited torsional states (ΔE1υt = 62.0183(13)cm−1; ΔE2υt = 120.3315(13)cm−1) with J ≤ 50 were included in the analysis that was performed employing the rho-axis-method (RAM), and the RAM36 code. A fit within experimental error (root mean square deviation equals to 35 kHz) has been achieved for this dataset using 47 parameters of the RAM torsion-rotation Hamiltonian. In the course of the analysis, it became evident that for such high ρ value, as it is determined for fluoral, a larger than usual torsional basis set at the first diagonalization step of the two-step diagonalization procedure is required for achieving a fit within experimental error., National French Programme “ANR Labex CaPPA” through the PIA (contract ANR-11-LABX-0005-01), Ministry of Science and Technology of Taiwan (grants MOST 104-2113-M-009-020 and MOST 105-2811-M-009-026)

The improvement of electronic device efficiency is currently based on the miniaturization of existing electronic devices. The manufacturing costs of reducing the size of semiconductor based circuits below 10 nm is unfeasible for companies. To overcome this limitation, other materials are currently being developed to fabricate equivalent electronic circuits with smaller dimensions. In this context, on-surface synthesis (OSS) is a bottom-up manufacturing technique based on the reaction of molecules to achieve a well-defined organic structure. The atomic precision of OSS allows to create functional organic molecules for molecular electronic devices. Scanning probe microscopy techniques are the most common microscopy techniques used to analyze on-surface synthesized structures. In this thesis, we present the synthesis by OSS and characterization by scanning tunneling microscopy (STM) and spectroscopy (STS) techniques of functional nanostructures. The synthesized manganese phthalocyanine (MnPc) includes in the phthalocyanine ring four diarylethylene moieties (DAE). The DAE moiety is an optically active group. This organo-metallic complex with optically active groups and the Mn in its structure could work as a magneto-optical transducer. We have successfully induced reversible switches with the STM tip between the assigned open and closed configurations of the DAE moiety. The other organic structures synthesized by OSS studied in this thesis are chiral graphene nanoribbons (ch-GNRs) on Ag(001). Combining STM and STS techniques we have studied the evolution of the electronic structure of ch-GNRs depending on their width and length. Furthermore, when the ch-GNRs are relocated on top of MgO monoloayers grown on the same Ag(001) substrate by means of atomic manipulation, a combination of charge transfer and electronic localization gives rise to a critical discretization of the extended edge states. This causes unprecedented long life times of the ribbon’s electronic states and spin splitting of the frontier orbitals ascribed to electron-electron correlations. Finally, we have evaluated the suitability of the ch-GNR/MgO monolayer/Ag(001) system as a molecular spin polarized transistor.

152 p. Water, the most abundant molecule in our planet, is truly and empirically accepted as an essential component to sustain life on Earth. The extraordinary properties of this unique and universal "matrix of life" have served over this quarter century, as the driving force -for theoreticians and experimentalists- to perform novel research on the structural basis and molecular dynamics taking place in very different environments. Even today, scientists are still discovering new phenomena in water, especially at the nanoscale.When referred to bio-systems, water is usually seen as the liquid environment -or "matrix"- where physical and chemical processes take place. Here, the molecules of life are thought of being wet - this is, completely immersed in liquid water or, in other words, in fully hydrated conditions. While this is true for most living cells, a surprising number of processes require merely traces of water, which could be vapor or a layer as thin as nanometers. Indeed, this is observed in situations in which, because of extremes of either heat or cold, liquid water is scarce. Here, the hydration layer of the molecules - understood as an entity that differs from bulk water - should confer certain stability to keep the biomolecules still functional; and the processes taking place at the air interface should play a prominent role.In this direction, the transmission of many airborne viruses - through respiratory droplets (e.g. aerosols) - requires, actually, survival in dry conditions. Influenza A virus (IAV), is one of the best-known cases, for which the transmission and thus survival is tightly connected to seasonal factors. Seasonal epidemics generally occur during winter, when air temperature and humidity are low. Under these conditions, the respiratory droplets must confer some structural stability to the contained viruses; membrane collapse, for example, should be in principle avoided. However, this assumption is yet poorly understood and experimental data based on biophysical methods are in great demand to obtain a solid knowledge base for the restriction of virus transmission (in addition to vaccination strategies).This thesis represents the outcome of almost four years of intensive work in the field of applied biophysics in life sciences. Here, we explore the possibilities to mimic IAV by different model systems, by mostly focusing on the role of hydration water under various relative humidity (RH) conditions, namely hydration scenarios. To date, RH has been one of the less investigated and one of the most controversial environmental factors. Its effect on the transmission, survival and stability of the virus is still under debate, while the influence of air temperature, e.g., is quite well established.In this research, the structure of the IAV envelope is studied in a range of model systems and by a combination of very different techniques, providing new biophysical insights on the micro- and nanoscale, from dehydrated to fully hydrated conditions. CICnanoGUNE CFM: Centro de Física de Materiales Universitat of Potsdam Fritz-Haber Institut of the Max Planck Society

One of the key aspects of photodynamic therapy is the light source that is used to irradiate the lesion to be treated. The devices used must ensure that their emission spectrum matches the absorption spectrum of the photosensitizer, so that treatment radiation is delivered only on the target area, without irradiating healthy tissue at superficial or deep levels. Irradiance values must be adequate in order to avoid thermal damage, exceed the oxygen replenishment rate and avoid long treatment times. Furthermore, the device should be user-friendly, inexpensive, and able to be adapted to different photosensitizers. We have developed an easy-to-use and highly customizable device based on LED technology. Its innovative geometric design allows radiation to be delivered to a small treatment surface, since the LEDs are arranged in three arms, the configuration of which directs their radiation on the treatment point. Different high-power color LEDs are disposed on the arms, and can be independently selected based on the most effective wavelengths for exciting the different photodynamic therapy photosensitizers. We have tested the prototype in 5 different patients (1 actinic keratose, 1 actinic cheilitis, 1 superficial basal cell carcinoma and 2 Bowen's disease) and after 1-2 sessions of total cumulative dose of 25-50 J / cm2, 100% clearance of lesions were obtained. Our device can be used by any professional in the field, whether for medical or research purposes. It facilitates the development of treatment protocols and trials with different photosensitizers.

En aquesta Tesi Doctoral s'han desenvolupat mètodes d'anàlisis basats en l'espectroscòpia en l'infraroig proper (NIR) i en l'espectroscòpia Raman per la seva aplicació en la indústria farmacèutica. En aquesta indústria, és necessari garantir la qualitat dels productes tant a la seva arribada com a la seva alliberació, procés que pot ser lent si s'empren tècniques tradicionals com el HPLC. Les alternatives espectroscòpiques utilitzades en aquest treball són tècniques ràpides i no destructives, que no requereixen l'ús de dissolvents i no generen residus. En molts casos, s'han usat instruments portàtils, tant NIR com IR, per comprovar el seu funcionament en comparació als equips de sobretaula. En la introducció, es descriuen les tècniques espectroscòpiques utilitzades, tant el seu fonament teòric com la seva instrumentació, i s'expliquen els mètodes quimiomètrics utilitzats, així com el procés de construcció dels models. La primera part de la Tesi està dedicada a la identificació de productes utilitzant diferents mètodes de reconeixement de pautes a espectres NIR i Raman, destacant la utilització d'una biblioteca en cascada. Fent ús d'ambdues tècniques espectroscòpiques i instruments portàtils, s'ha estudiat la identificació de comprimits de diferents marques comercials, amb igual principi actiu, però fabricats per diferents laboratoris. S'ha pogut discriminar segons l'origen de fabricació. En un altre capítol, s'ha construït i validat, interna i externament, una biblioteca d'espectres NIR que assegura la identitat de 436 materials de partida que es reben en una indústria farmacèutica. Durant el desenvolupament, s'ha ensenyat com resoldre problemes habituals en construir aquest tipus de biblioteques. A més, s'ha elaborat una anàlisi de riscos per disminuït els falsos negatius de productes fora d'especificació, avaluant el risc de cada factor identificat i proposant accions mitigadores, en cas necessari. Amb els resultats obtinguts quotidianament en la recepció dels productes en la indústria, s'ha avaluat el comportament de les biblioteques desenvolupades i el resultat de l'aplicació de les accions per disminuït els falsos negatius. En la segona part de la Tesi s'ha determinat la concentració d'APIs en producte acabat, i estudiar l'aplicació de les tècniques espectroscòpiques per assegurar la uniformitat de contingut (UC) de dosis en APIs. Utilitzant l'espectroscòpia Raman i un instrument portàtil, s'ha determinat la concentració d'ibuprofèn en un gel comercial. Els pretractaments del senyal duts a terme permeten emprar un mètode de calibració univariant. A més, emprant la mateixa tècnica, però amb un instrument de sobretaula, s'ha suggerit un mètode per determinar la UC de dosis en comprimits sencers i en les fraccions en les quals es pot dividir; s'ha optimitzat el nombre mínim de mesures que proporcionen un resultat correcte a pesar de la possible agregació del API en comprimits. Finalment, s'ha estudiat la determinació simultània d'APIs que es troben junts en el mateix comprimit, però en condicions de gran desproporció entre les seves concentracions, fet que pot provocar que la contribució del majoritari en l'espectre influeixi en la determinació del minoritari. Per això, s'han utilitzat mesures NIR realitzades amb un instrument de sobretaula i un portàtil, per estudiar les diferències en els resultats obtinguts amb ambdós instruments en el cas de quantificacions complexes. S'ha emprat un mètode de calibració multivariable amb bons resultats i s'ha aplicat a l'estudi de la UC de dosis. En esta Tesis Doctoral se han desarrollado métodos de análisis basados en la espectroscopia en el infrarrojo cercano (NIR) y en la espectroscopia Raman para su aplicación en la industria farmacéutica. En esta industria, se requiere garantizar la calidad de los productos tanto a su llegada como a su liberación y puede ser un proceso lento cuando se utilizan técnicas tradicionales como HPLC. Las alternativas espectroscópicas utilizadas en este trabajo son técnicas rápidas y no destructivas, que no requieren el uso de disolventes y no generan residuos. En muchos casos se ha empleado equipos portátiles, tanto NIR como IR, para comprobar su desempeño frente al de los equipos de sobremesa. En la introducción, se describen las técnicas espectroscópicas empleadas, tanto su fundamento teórico como su instrumentación; y se explican los métodos quimiométricos utilizados, así como el proceso de construcción de los modelos. La primera parte de tesis está dedicada a la identificación de productos utilizando distintos métodos de reconocimiento de pautas a espectros NIR y Raman, destacando la utilización de bibliotecas en cascada. Utilizando ambas técnicas espectroscópicas y equipos portátiles, se ha estudiado la identificación de comprimidos de distintas marcas comerciales, con el mismo principio activo, pero fabricados por distintos laboratorios. Se han podido discriminar según el origen de fabricación. En otro capítulo se ha construido y validado, interna y externamente, una biblioteca de espectros NIR que garantiza la identidad de 436 materiales de partida que se reciben en una industria farmacéutica, mostrando cómo solventar los problemas habituales que surgen en la construcción de este tipo de bibliotecas. Se ha realizado un análisis de riesgos para disminuir los falsos negativos de productos fuera de especificaciones, evaluando el riesgo de cada factor y proponiendo acciones mitigadoras de dicho riesgo en caso necesario. Con los datos obtenidos cotidianamente en la recepción de productos en la industria, se ha evaluado el comportamiento de las bibliotecas construidas y el resultado de la aplicación de las acciones para disminuir los falsos negativos. En la segunda parte de la tesis se ha determinado la concentración de APIs en producto acabado y la aplicación de las técnicas espectroscópicas para asegurar la uniformidad de contenido de la dosis del API. Utilizando espectroscopia Raman y un instrumento portátil, se ha determinado la concentración de ibuprofeno en un gel comercial. Los pretratamientos de la señal realizados permiten utilizar un método de calibración univariante. También utilizando espectroscopia Raman, pero con un instrumento de sobremesa, se ha propuesto un método para determinar la uniformidad de contenido de dosis en comprimidos enteros y en las fracciones en las que se puede dividir; se ha optimizado el número mínimo de medidas que proporcionan un resultado correcto a pesar de la posible agregación del API en el comprimido. Finalmente, se ha estudiado la determinación simultánea de APIs que se encuentran juntos en el mismo comprimido, pero en condiciones de gran desproporción entre sus concentraciones, lo que puede ocasionar que la contribución al espectro del compuesto mayoritario influya en la determinación del minoritario. Para ello se han utilizado medidas NIR, realizadas tanto con un equipo de sobremesa como con un equipo portátil, para estudiar las diferencias en los resultados obtenidos con ambos tipos de equipos en caso de cuantificaciones complejas. Se ha utilizado un método de calibración multivariable con buenos resultados y se ha aplicado al estudio de uniformidad de contenido de dosis. In this Doctoral Thesis, analysis methods based on near-infrared (NIR) and Raman spectroscopy have been developed for their application in the pharmaceutical industry. In this industry, it is necessary to ensure the quality of all products in both their reception and release. Such necessity could be a slow process when using traditional techniques such as HPLC. The spectroscopic techniques are a great alternative to conventional methods as they are fast and non-destructive, without the need for solvents, and no generation of residuals. In most cases, portable instruments, both NIR and IR, have been employed to assess their performance over the benchtop ones. The introduction presents a summary of the fundamentals and instrumentation of the spectroscopic techniques employed. Furthermore, the chemometric methods and the steps followed to construct them are also explained. The first part of the Thesis is dedicated to the identification of products using different pattern recognition methods and NIR and Raman data. In this part, the use of cascading libraries is highlighted. First, using both spectroscopic techniques and portable instruments, the identification of tablets commercialized by different industries has been studied. These samples contain the same API but are produced by several laboratories. Hence, it has been possible to discriminate against them according to their origin. Second, a NIR spectral library has been constructed and validated, internally and externally, to identify 436 raw materials received in the pharmaceutical industry. Therefore, it has been demonstrated how to solve usual problems when constructing these libraries. In addition, a risk analysis has been performed to reduce the number of false positives when using these libraries. Hence, the risk of each factor has been studied and mitigation actions proposed. The performance of the library and the mitigation actions have been evaluated with the results of new raw materials identification. The second part of the Thesis is related to the determination of the API concentration in finished products and ensuring API dose content uniformity (CU). First, the content determination of ibuprofen in gel samples has been carried out. This determination is performed using Raman spectroscopy and one portable instrument. The signal pretreatment performed allows using a univariate calibration method. Second, with the use of Raman spectroscopy and a benchtop instrument, a method to determine the CU of tablets has been proposed. This method allows the measure of CU in the entire tablet and their fractions. Therefore, the minimum number of measures to obtain adequate results has been optimized even though the possible aggregation of the API. Finally, the simultaneous determination of two APIs in the same tablets has been performed. Both APIs are at a high different mass proportion, which may interfere in the determination of the minority API. Thus, NIR measurements obtained with portable and benchtop instruments are used to quantify both APIs. In this case, a multivariable calibration method has been used to construct the methods. Hence, the CU has also been determined and, the results of both instruments compared.

Orientador: Munemasa Machida Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin Resumo: Os plasmas DBD, Descargas com Barreira de Dielétrico, em pressões atmosféricas têm despertado grande interesse nas pesquisas nos últimos anos, principalmente pelas suas aplicações práticas: deposição de materiais, tratamento de superfícies, tratamento de cáries, esterilização de bactérias e destruição de células cancerígenas. Estes plasmas são chamados de plasmas não-térmicos e diferem dos plasmas de alta temperatura (estelares e de reatores de fusão nuclear) e dos plasmas térmicos (tochas de plasmas e plasmas industriais), por possuírem temperaturas translacional, eletrônica, vibracional e rotacional distintas. Para determinar a temperatura de plasmas DBD em descargas elétricas nos gases Ar e He, utilizamos um método indireto que avalia a temperatura por meio de um plasma de Nitrogênio molecular formado pela colisão dos plasmas de Ar e He com o Nitrogênio presente no ar. O espectro luminoso deste plasma é medido, as principais linhas de emissão catalogadas e depois analisado com um software específico para determinação de temperaturas de gases moleculares. Também são mostradas aqui algumas das principais técnicas de espectroscopia usadas na captação de espectros luminosos de plasmas laboratoriais, realizadas em dois dispositivos, plasma DBD produzido com jato de seringa, e plasma fracamente ionizado produzido com uma descarga DC entre dois eletrodos Abstract: Research on DBD (Dieletrical Barrier Discharges) plasmas at atmospheric pressure have attracted attention and great interest on its research upon the last few years, mostly because of its practical applications: material deposition, surface treatment, cavity treatment, bacterial sterilization and cancer cell destruction. These plasmas are called nonthermal plasmas and differ from the high temperature plasmas (stellar and fusion reactors) and thermal plasmas (plasma torches and industrial plasmas) because of its distinct translational, electronic, vibrational and rotational temperatures. For temperature determination in DBD plasmas formed by electrical discharges on Ar and He gases, an indirect method is used evaluating the temperature of molecular nitrogen plasma formed by collision between the Ar and He plasmas with the nitrogen present in air. The luminous specter of this plasma is measured, the principal emission lines cataloged and then analyzed with specific software for molecular gases temperature determination. The main spectroscopic techniques used for analysis of the luminous spectra obtained from two devices: DBD plasma generated by a syringe jet and weakly ionized plasma produced by a DC discharge between two electrodes, are show on this thesis Mestrado Física Mestre em Física

Orientador : Yoshitaka Gushikem Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica Mestrado

Orientador: Artemio Scalabrin Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin Resumo: A técnica de geração de radiação eletromagnética coerente por moléculas polares bombeadas opticamente têm-se mostrado muito eficiente e de grande importância nos últimos anos, pelas suas inúmeras e únicas aplicações. Neste trabalho utilizamos amostras de CH3OH, 13CH3OH, CD3OH e CD3OD como meio ativo buscando novas linhas laser IVL e, através do modelo de Vibração-Rotação-Rotação Interna, a identificação de parâmetros espectroscópicos importantes nessa ação Laser. Para o CH3OH, doze novas linhas foram encontradas, com a identificação completa dos números quânticos e níveis de energia associados a duas delas. Com a amostra de 13CH3OH obtivemos um numero de 36 novas linhas laser IVL das quais 10 puderam ser completamente identificadas. Dúvidas pré existentes em relação a linhas laser IVL em CD3OH puderam ser eliminadas através de um trabalho revistivo com essa molécula, que, como conseqüência, apresentou a descoberta de 69 novas linhas. Uma nova interpretação espectroscópica para as moléculas que participam na ação laser IVL em CD3OH é apresentada, permitindo a identificação completa de 52 dessas transições. CD3OD, é a molécula que apresenta o maior número de novas linhas laser IVL observadas neste trabalho: 80. Destas, nenhuma pôde ser identificada já que os parâmetros moleculares associados no modo de estiramento C-O dessa molécula não são determinados. Analisa-se também, a viabilidade de utilização dessas linhas laser em novos experimentos. Em particular, discute-se sua utilização em diagnóstico de plasmas de interesse termonucleares através da técnica polarimétrica e de um sistema óptico apropriado e proposto por nós. Esse sistema faz uso do fato do plasma comportar-se como um meio birrefringente e opticamente ativo permitindo a determinação simultânea de parâmetros tais como a densidade eletrônica e o campo magnético poloidal para uma configuração de Tokamak, e da densidade eletrônica. e/ou campo magnético para um q-pinch Abstract: We worked with , 13CH3OH, CD3OH and CD3OD molecules as active medium for obtaining new FIR laser lines and assignments by the optical pumping method with a c.w. CO2 laser. For the CH3OH, 12 new laser lines are observed, with 2 assigned completely. For 13CH3OH molecule, 36 new FIR laser lines were found and 10 of then were assigned completely. Previous doubts related to the FIR laser lines in CD3OH, were eliminated through a review work with this molecule and as a consequence 69 new FIR laser lines were discovered. A new spectroscopic interpretation for the participating molecules in this laser action is presented allowing complete assignment of 52 transitions CD3OD is the molecule that shows the greater number of new FIR laser lines: 80. We couldn¿t assign these lines due to the inexistence of molecular parameters associated to C-O stretching. We also study the possibility of using the se lines for new experiments. In particular we discuss their use in plasma diagnostics with the polarimetric technique and propose an appropriate optical system. This system is based in the fact that a magnetized plasma behaves as a birefringent and optically active medium allowing a simultaneous determination of some parameters as the electronic density and the poloidal magnetic field for a Tokamak configuration and also the electronic density and/or the magnetic field for a q-Pinch configuration Doutorado Física Doutor em Ciências

Orientadores: Jose Inacio Cotrim Vasconcellos, Nilce Correa Meirelles Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin Resumo: É apresentado neste trabalho um estudo comparado entre as moléculas de hemoglobina humana A, humana S e de Ranacatesbeiana. Utilizamos para este estudo duas técnicas: a espectroscopia de absorção óptica ( visível e infravermelho ) e a espectroscopia fotoacústica ( visível ). Com as amostras na forma de solução aquosa foram obtidos espectros de absorção óptica no intervalo espectral de 250nm a 600nm e fotoacústicos no intervlo de 300nm a 600nm. Para a obtenção dos espectros na região do infravermelho ( 2,5u a 40u ) foram utilizadas amostras na forma de cristais ou liofilizados prensadas num disco de KBr. Após a obtenção dos dados experimentais foi feita a deconvolução dos espectros e um ajuste computacional das linhas obtidas tentando caracterizá-las através da frequência ou comprimento de onda de absorção máxima, largura e forma. É traçado um estudo comparado entre as diferentes hemoglobinas no mesmo intervalo espectral e são lançadas bases comparativas entre os espectros fotoacústicos e de absorção óptica Abstract: Not informed Mestrado Física Mestre em Física

Orientador: Yoshiyuki Hase Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica Mestrado

Orientador: Arnaldo Naves de Brito Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin Resumo: Este trabalho apresenta estudos em física atômica e molecular, tanto teóricos quanto experimentais. Foram realizados cálculos de forças de osciladores ponderadas para os seguintes íons de silício: Si I, Si XI, Si XII e Si XIII. Estes cálculos são realizados em uma aproximação relativística multiconfiguracional Hartree-Fock. Os parâmetros eletrostáticos foram otimizados por um procedimento de mínimos quadrados, para um melhor ajuste com dados experimentais de níveis energéticos e comprimentos de onda de transições. Um outro trabalho na área de física atômica foi a construção de um novo espectrômetro de massa por tempo de vôo para medidas de momento de recuo de íons em átomos resfriados com laser, após fotoionização por radiação síncrotron. Este é um trabalho pioneiro que abre uma nova linha de pesquisa. Com este equipamento foram realizadas medidas de momento de recuo em íons Cs + , e foi possível também a obtenção do parâmetro de assimetria b para as energias estudadas, entre 13 e 40 eV. Os estudos em física molecular compreenderam medidas de multicoincidência elétron-íon (PEPICO ¿ PhotoElectron-PhotoIon COincidence) e elétron-íon-íon (PEPIPICO ¿ PhotoElectron-PhotoIon-PhotoIon COincidence) em N2 e O2 próximas aos limiares de ionização N 1s e O 1s, respectivamente. Espectros de produção total de íons também foram obtidos para estas moléculas. Foram realizadas também medidas de coincidência elétron-íon (PEPICO) para alguns aminoácidos em sua forma gasosa pela primeira vez Abstract: This thesis comprises atomic and molecular physics studies, both theoretical and experimental. Weighted oscillator strengths and lifetimes were calculated for the following silicon ions: Si I, Si XI, Si XII and Si XIII. The calculations were carried out in a multiconfiguration Hartree-Fock relativistic aproach. The eletrostatic parameters were optimized by a least-squares procedure in order to improve the adjustment to experimental energy levels and transitions wavelengths. Another work in the atomic physics area was the construction of a new time-of-flight spectrometer to measure ion recoil momentum in laser-cooled atoms, after photoionization by synchrotron radiation. This is a pioneering work that opens up a new research area. With this equipment ion recoil momentum were measured for the Cs + ion, and it was possible to determine the b assymetry parameter in the energy range studied, 13 to 40 eV. The molecular physics studies comprised multicoincidence measurements (PEPICO and PEPIPICO) in N2 and O2 near the ionization thresholds N 1s and O 1s, respectively. Total Ion Yield (TIY) spectra were also obtained for these molecules. Coincidence spectra (PEPICO) for some aminoacids in their gas phase were also taken for the first time Doutorado Física Doutor em Ciências

Orientadores: Arnaldo Naves de Brito, Antonio Rubens Britto de Castro Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin Resumo: O objetivo principal desta tese é estudar os processos de foto-fragmentação seletiva de moléculas livres excitadas por radiação síncrotron usando espectroscopia de multicoincidência. Abaixo estão resumidas algumas contribuições originais e de importância deste trabalho: 1) Apresentamos pela primeira vez evidências experimentais da ocorrência de dissociação ultra-rápida na molécula de água após a excitação O1s ® 4a1. Antes deste trabalho, havia na literatura uma controvérsia onde vários autores apontavam um caráter não-ligante para o orbital 4a1. Nosso estudo apresenta uma evidência clara do caráter anti-ligante deste orbital. Outro ponto importante foi ter apresentado um método inédito para o estudo da dissociação ultra-rápida utilizando espectroscopia de multicoincidência. 2) Apresentamos pela primeira vez um estudo comparativo dos vários canais de dissociação da molécula de ozônio utilizando a técnica de multicoincidência na faixa de 12 a 21 eV de energia do fóton. 3) Evidenciamos como o movimento nuclear no estado intermediário junto com a localização dos estados de caroço pode levar à dissociação seletiva da molécula de ozônio. Nos estudos de dissociação seletiva de moléculas é apontada como altamente desejável a observação de mudanças no padrão de dissociação em função do número quântico vibracional do estado intermediário. Embora no caso do ozônio os níveis vibracionais dos vários modos normais impeçam a identificação individual de cada estado vibracional, é possível escolher um grupo destes estados vibracionais. Ao escolher diferentes grupos estamos variando a energia interna do estado intermediário. Uma das grandes contribuições desta tese foi demonstrar que para o ozônio diferentes padrões de fragmentação foram observados em função do grupo de estados vibracionais populados no estado intermediário. Isto foi interpretado como uma demonstração de que o movimento nuclear no estado intermediário cujo tempo de vida é de poucos fentossegundos pode influenciar o padrão de dissociação após a ionização de elétrons de orbitais de camada interna. 4) Utilizando uma nova estação experimental, desenvolvida no LNLS, demonstramos que mesmo para algumas moléculas poliatômicas a excitação de elétrons de orbitais de camadas internas levam ao quase-alinhamento destas moléculas. Tal alinhamento ocorre em relação à direção do vetor campo elétrico de polarização do feixe de luz síncrotron. Uma das consequências deste estudo é que um melhor conhecimento da energia cinética de quebra de algumas da ligações destas moléculas pode ser obtido. Informação da simetria local de alguns orbitais desocupados também pode ser obtida. 5) Apresentamos também um trabalho de instrumentação no analisador de elétrons utilizado nas medidas do artigo 3. Este trabalho resultou em aumento na resolução do analisador de elétrons que permitiu a realização dos estudos descritos sobre o ozônio. A melhora na resolução foi consequência do desenvolvimento de um novo sistema de lentes eletrostáticas Abstract: The main purpose of this thesis is to study selective photo-fragmentation processes of free molecules excited by synchrotron radiation using multi-coincidence spectros-copy. Below are summarized some original and important contributions of this work: 1) We show for the first time experimental evidences of ultrafast dissociation in water molecule after O1s ® 4a1 excitation. Before this work there was in the literature a controversy where many authors pointed to the non-bonding character of the 4a1 orbital. Our study present a clear evidence of the anti-bonding character of this orbital. Another important point was the presentation of a new method to study ultrafast dissociation using multi-coincidence spectroscopy. 2) We presented for the first time a study about the dissociation channels of the ozone molecule using the multi-coincidence technique between 12 and 21 eV photo excitation energy. 3) We show in a clear way how the nuclear movement in the intermediate state together with the localization of core states can lead to the selective dissociation of the ozone molecule. In the studies of selective dissociation of molecules it is desirable to observe changes in the pattern of dissociation as a function of the vibrational quantum number of the intermediate state. Although, in the case of ozone the vibrational levels of many normal modes inhibit the individual identification of each vibrational state it is possible to choose a group of this states. By selecting different groups we change the internal energy of the intermediate state. One of the main contributions of this thesis was the observation of changes in the dissociation patterns when different groups of vibrational states were populated in the intermediate state of ozone. These changes demonstrate that the nuclear movement in the intermediate state, which has lifetime of few femtoseconds, can influence the dissociation pattem after electron ionization from inner shell orbital. 4) A new experimental chamber developed at LNLS was used to demonstrate that (even for some polyatomic molecules) the excitation from inner shell orbital leads to the quasi-alignment of this excited molecules. Such alignment occurs with respect to the electric field polarization vector of the synchrotron light. One of the consequences of this study is a better knowledge of the kinetic energy released in the dissociation. The local symmetry of the unoccupied orbital of the molecules can also be obtained. 5) We presented also an instrumentation study in the electron analyzer used in the measurements of article 3. This work provided a substantial improvement of the electron analyzer resolution allowing the realization of the studies performed with ozone. The resolution achieved was due the development of a new electrostatic lens system Doutorado Física Doutora em Ciências

Orientador : Roy E. Brums Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica Doutorado

96 p. La química orgánica es un campo de investigación extremadamente maduro cuyos continuos avances han ido permitiendo la generación de materiales cada vez más refinados, caracterizados por fascinantes propiedades físicas y químicas. La aplicación de tales compuestos orgánicos nanoestructurados ha ido generando importantes impulsos al campo de la nanociencia. En los últimos 15 años se está desarrollando una nueva alternativa a la química convencional: la síntesis en superficies (¿on-surface synthesis¿, OSS) bajo condiciones de ultra alto vacío. Este nuevo planteamiento ha abierto nuevas puertas para la formación de nanoestructuras de carbono que no están al alcance de los métodos convencionales. Su aplicación para la síntesis de materiales orgánicos de baja dimensionalidad y con precisión atómica está mostrando un crecimiento en auge y tiene un enorme potencial para aplicaciones que incluyen nuevas tecnologías cuánticas.En esta tesis, este novedoso enfoque se aplica al crecimiento de diferentes tipos de materiales, seguido de una caracterización integral de las propiedades estructurales, químicas y electrónicas de los productos intermedios y finales. Para tal fin se ha utilizado principalmente la microscopía túnel de barrido a baja temperatura (4,3 K) en varios modos de medición, complementados con cálculos teóricos (DFT y métodos de partículas de sonda). En concreto se han estudiado los siguientes sistemas:(i) Química metal-orgánica, en la que se muestra la manera de controlar la estructura de enlace de tiolatos de oro y su estereoespecíficidad variando los parámetros de reacción en la superficie (recubrimiento y temperatura del sustrato).(ii) Química basada en pirenos. Usando moléculas de pireno funcionalizadas con alquinos, se investiga el efecto de los complejos metal-orgánicos descritos anteriormente en las reacciones de acoplamiento de alquinos. Los complejos metal-orgánicos no solo modifican el resultado de la reacción, sino que también reducen el umbral de la temperatura de activación, siendo por tanto un excelente ejemplo de síntesis en superficie de segundo orden (es decir, OSS del catalizador para dirigir nuevas reacciones de OSS). De otro lado, también se han utilizado pirenos funcionalizados con dos tipos de grupos funcionales distintos, como son los alquinos y átomos de Br. La presencia de ambos grupos funcionales permite nuevo abanico de reacciones que incluyen el tanto el acoplamiento de alquinos o el acoplamiento cruzado. El análisis de los productos resultantes y su abundancia tras tratamientos de calentamiento muestran una dominancia del acoplamiento de Glaser (acoplamiento de alquinos con pérdida de hidrógeno) como reacción inicial. Sin embargo, al utilizar un precursor no halogenado se observa una prevalencia de un acoplamiento sin pérdida de hidrógeno y una total ausencia de acoplamiento Glaser, evidenciando el papel crítico del Br en la reactividad de alquinos. Es importante destacar también que una comparación sistemática de las propiedades electrónicas de las diferentes estructuras de los productos ha permitido trazar importantes relaciones entre la estructura y las propiedades de los diversos tipos de acoplamientos entre pirenos.(iii) Química basada en aceno. Se ha estudiado la síntesis de acenos de gran tamaño, en concreto de heptaceno sobre Ag(001), a partir de precursores moleculares de tetrahidroheptaceno con y sin funcionalización adicional por átomos de Br. Se ha encontrado una variedad de productos intermedios que a menudo resultan de eventos de migración de hidrógeno. Sin embargo, el heptaceno es el producto final de los dos precursores y muestra un orbital LUMO completamente cargado. Centrándonos en los intermedios, se observa cómo dos átomos de carbono con hibridación sp3 en el segundo anillo de dihidroheptaceno son suficientes para causar el auto-desacoplamiento electrónico de la molécula y el sustrato. Se han investigado asimismo las señales magnéticas, evidenciadas en resonancias Kondo, asociadas a determinados escenarios de carga. Finalmente, utilizando precursores basados en acenos se ha explorado el impacto del sustrato en las reacciones de acoplamiento. En concreto se han utilizado superficies de Au(111) y Au(110), así como precursores de antraceno funcionalizados con halógenos y metilos. Sobre Au(111), una superficie atómicamente plana, se encuentran cinco tipos de productos covalentes, siendo el starphene con simetría de eje ternario el producto dominante. Por contra, sobre la superficie reconstruida de Au(110) 2×1, su simetría uniaxial promueve la formación de polímeros lineales no benzenoides.Esta tesis contribuye al campo de la ciencia de superficies, mostrando la posibilidad de sintetizar una variedad de nanomateriales novedosos basados en carbono mediante la síntesis en superficie, así como mediante la caracterización detallada sus propiedades. La comprensión de las propiedades físico-químicas de estos materiales avanzados es un paso de gran relevancia hacia sus futuras aplicaciones. The mature research field of conventional solution-based chemistry has allowed for a continuous generation of increasingly refined materials with amazing physical and chemical properties. This has contributed to great advances in the field of organic nanomaterials. The development of the recently revealed surface-supported synthesis under ultrahigh vacuum conditions has opened new doors for the formation of defect-free low-dimensional carbon nanostructures that are not achievable by conventional means. This new field, typically termed on-surface synthesis (OSS), is lately showing a booming growth that resonates with almost all the requirements for promising quantum size materials with tunable physicochemical properties.In this thesis, this novel approach is applied for the growth of a variety of materials, followed by a comprehensive characterization of the structural, chemical and electronic properties of the intermediates and end-products. This is achieved mainly by scanning tunneling microscopy operating at low temperature (4.3 K) in various measurement modes, assisted by theoretical calculations (DFT and probe particle methods). In particular, the following systems have been studied:(i) Metal-organic chemistry, in which the stereospecific coupling motif of gold thiolates is found to be controllable by varying the on-surface reaction parameters (i.e. coverage and substrate temperature).(ii) Pyrene-based chemistry. With alkyne-functionalized pyrene molecules, the impact of the presence of metal-organic complexes on alkyne coupling reactions is investigated. The complexes do not only modify the reaction outcome, but also reduce its activation temperature threshold, becoming an excellent example of second-order on-surface synthesis (i.e. OSS of catalyst to steer following OSS reactions). Secondly, pyrenes are used that are functionalized with alkynes and also Br atoms, allowing for alkyne homo- and cross-coupling reactions. The resulting products and their relative abundance are explored thoroughly after different annealing steps, revealing a dominant Glaser-coupling product upon heating. The absence of the latter when using non-halogenated precursor evidenced the role of Br in this coupling reaction. Importantly, a systematic comparison of the electronic properties of the different product structures has allowed drawing important structure-property relations with regard to the various inter-pyrene coupling motifs.(iii) Acene-based chemistry. The synthesis of higher acenes is studied, in particular heptacene on Ag(001), starting from tetrahydroheptacene molecular precursors with and without additional functionalization by Br atoms. A variety of stable reaction intermediates is found, often resulting from hydrogen migration events. However, heptacene is the end-product from the two precursors and displays a fully charged LUMO orbital. Focusing on the intermediates, two sp3-hybridized carbon atoms present at the second ring of dihydroheptacene are shown as sufficient self-decoupling factors. Magnetic Kondo fingerprints associated to specific charging scenarios are investigated. Finally, the impact of the surface structure on coupling reactions with acene-based precursors is then explored. More specifically, Au(111) and Au(110) surfaces, as well as anthracene precursors functionalized with halogen and methyls are used with this aim. On Au(111), the atomically flat surface, five covalent coupling motifs are found, with the 3-fold symmetric starphene showing the highest occurrence upon annealing. In contrast, on Au(110), being a 2×1 reconstructed surface, the uniaxial symmetry of the surface promotes the formation of mainly linear non-benzenoid polymers along the grooves of this substrate.This thesis contributes to the surface science field by showing the possibility to synthesize a variety of novel carbon-based nanomaterials using on-surface synthesis methods. The second main contribution is the detailed characterization of the produced materials using surface-sensitive techniques assisted by theoretical calculations. A deep understanding of the physicochemical properties of these materials is a crucial step forward towards their ultimately progressing applications. CFM; CSIC

258 p.(eng.) 144 p. (eusk.) La química de colorantes está presenciando un renovado reconocimiento como herramienta valiosa para diseñar materiales fotónicos inteligentes prácticos. Las recientes rutas sintéticas en química orgánica han permitido el acceso a nuevas estructuras moleculares, en particular las hechas a la medida. En este contexto, nuestro objetivo en esta tesis es diseñar, caracterizar y aplicar una nueva generación de colorantes orgánicos como fluoróforos y fotosensibilizadores con fines fotónicos. En lugar de usar diferentes colorantes para cada propósito de aplicación, la estrategia empleada aquí se basó en el uso de un punto de partida molecular específico, donde, tras adecuadas modificaciones químicas de su núcleo coromofórico, la función fotónica pudo ser modulada de una manera controlada dependiendo del campo de aplicación que se quería perseguir. Es por ello que se eligió el colorante BOro DIPYrrometeno (BODIPY) como patrón molecular para hacer frente a diferentes aplicaciones fotónicas, incluso cuando a veces implicaban propiedades fotofísicas opuestas. Un diseño lógico de su estructura molecular permite el desarrollo de colorantes capaces de emitir en la región roja e infrarroja cercana para ser aplicados como láseres sintonizables, sensores fluorescentes para la detección de biomoléculas, y pruebas fluorescentes para bioimagen, así como fotosensibilizadores no fluorescentes capaces de generar oxigeno singlete para terapia en biomedicina. Su diseño se amplió a través de la combinación de numerosos colorantes en una única estructura molecular, donde los nuevos fenómenos fotofísicos como la transferencia de energía y carga, y los acoplamientos excitónicos, son impulsados. Estos colorantes multicromofóricos complejos y desafiantes presentan un comportamiento excepcional como láseres de colorante mejorados, sistemas ópticamente activos, captadores de luz y antenas moleculares.

The introduction of a novel tetra‐ortho‐chloroazobenzene amino acid (CEBA) has enabled photoswitching of the antimicrobial activity of tyrocidine A analogues by using exclusively visible light, granting spatiotemporal control under benign conditions. Compounds bearing this photoswitchable amino acid become active upon irradiation with red light, but quickly turn‐off upon exposure to other visible light wavelengths. Critically, sunlight quickly triggers isomerisation of the red light‐activated compounds into their original trans form, offering an ideal platform for self‐deactivation upon release into the environment. Linear analogues of tyrocidine A were found to provide the best photocontrol of their antimicrobial activity, leading to compounds active against Acinetobacter baumannii upon isomerisation. Exploration of their N‐ and C‐termini has provided insights into key elements of their structure and has allowed obtaining new antimicrobials displaying excellent strain selectivity and photocontrol., A novel photoswitchable amino acid has provided access to tyrocidine A analogues fully operated under visible light. This has led to linear analogues that have shown good photoswitchability and strain selectivity against A. baumannii and S. pyogenes clinical strains by using different analogues. Activated cis compounds turn back to their deactivated trans form upon short exposure times to sunlight, paving the way to self‐deactivating antibacterials with minor evolutionary pressure on the environment.

El estudio y comprensión de las interacciones no covalentes a nivel molecular es un campo que está en continuo desarrollo y cobra vital importancia para determinar el comportamiento estructural de muchas moléculas de interés químico, tecnológico o biológico. En esta tésis doctoral se han analizado las interacciones intermoleculares implicadas en la formación de agregados moleculares neutros, tanto dímeros como productos de microsolvatación, en fase gas. Los complejos intermoleculares se han generado mediante expansiones supersónicas pulsadas, caracterizándose posteriormente mediante espectroscopía de rotación. Este trabajo ha utilizado dos técnicas espectroscópicas, incluyendo un espectrómetro de microondas con transformada de Fourier (FTMW) de tipo Balle-Flygare en el rango de frecuencias 8-20 GHz, y un espectrómetro de transformada de Fourier de banda ancha con excitación multifrecuencia (CP-FTMW) cubriendo el rango espectral de 2-8 GHz. Los complejos intermoleculares estudiados han incluido moléculas con grupos alcohol y/o tiol, con objeto de analizar las diferencias entre las interacciones intermoleculares que implican átomos de oxígeno o azufre, en especial el enlace de hidrógeno. Se han estudiado moléculas incluyendo tanto sistemas cíclicos alifáticos (ciclohexanol, ciclohexanotiol) como aromáticos (furfuril alcohol, furfuril mercaptano, tienil alcohol, tienil mercaptano). Los enlaces de hidrógeno analizados han comprendido especialmente interacciones de tipo O-H···O, O-H···S y S-H···S. La formación de los complejos intermoleculares ha revelado en algunos de ellos una gran variedad conformacional, como la observación de seis isómeros del dímero de ciclohexanol. En el caso de los monohidratos se han observado en algunos casos desdoblamientos asociados a movimientos internos de gran amplitud, como la rotación de la molécula de agua en los monohidratos de ciclohexanol y tienil mercaptano. En los casos de moléculas quirales la dimerización ha permitido observar la estabilidad relativa de los diastereoisómeros homo o heteroquirales. El estudio experimental se ha completado con diferentes cálculos teóricos de orbitales moleculares, en especial teoría del funcional de la densidad, a fin de caracterizar las interacciones estructuralmente, energéticamente y mediante análisis topológico de la densidad electrónica. El conjunto de datos experimentales y teóricos permite aumentar la información existente sobre enlaces de hidrógeno con átomos de azufre, generalmente poco estudiados, y su comparación con los análogos oxigenados., The study and understanding of non-covalent interactions at molecular level is a field in continuous development and essential to determine the structural behavior of many molecules of chemical, technological or biological interest. In this PhD thesis, the intermolecular interactions involved in the formation of neutral molecular aggregates, both dimers and microsolvation products, have been analyzed in the gas phase. The intermolecular complexes were generated by pulsed supersonic expansions, and later characterized by rotational spectroscopy. This work has used two spectroscopic techniques, including a Balle-Flygare Fourier-Transform Microwave (FTMW) spectrometer in the 8-20 GHz frequency range, and a broadband Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectrometer covering the 2-8GHz spectral range. The intermolecular complexes studied have included molecules with alcohol and / or thiol groups, in order to analyze the differences between the intermolecular interactions involving oxygen or sulfur atoms, especially hydrogen bonds. Molecules that comprise both aliphatic (cyclohexanol) and aromatic (furfuryl alcohol, furfuryl mercaptan, thenyl alcohol, thenyl mercaptan) ring systems have been studied. The analyzed hydrogen bonds included especially O-H···O, O-H···S and S-H···S interactions. The formation of intermolecular complexes has revealed a great conformational diversity in some of them, such as the observation of six isomers of the cyclohexanol dimer. With regard to the monohydrates, tunnelling splittings associated with internal large amplitude motions have been observed in some cases, such as the rotation of the water molecule in the monohydrates of cyclohexanol, thenyl alcohol and thenyl mercaptan. In the case of chiral molecules, dimerization has made it possible to observe the relative stability of homo- or heterochiral diastereoisomers. The experimental study has been supported by different theoretical molecular orbital calculations, in particular Density Functional Theory (DFT) calculations, in order to characterize the interactions structurally, energetically and by a topological analysis of electron density. The set of experimental and theoretical data will advance the existing information on hydrogen bonds involving sulfur atoms, generally scarcely studied, and their comparison with the oxygenated analogues., Departamento de Química Física y Química Inorgánica, Doctorado en Física

268 p. (eng.) 147 p. (eusk.) En el presente proyecto de tesis se presenta un extenso estudio sobre la caracterización de agregados moleculares de distinto interés biológico. Concretamente, la tesis se centra en la determinación estructural de dichos agregados y en el análisis de las interacciones no-covalentes. Éstas fuerzas son ubicuas en la naturaleza, y gobiernan una plétora de procesos químicos, industriales y biológicos, que abarcan desde la formación de pequeños agregados moleculares, hasta fenómenos supramoleculares de gran escala, como la formación de aerosoles, el plegado de proteínas o el reconocimiento molecular. Sin embargo, estas fuerzas son muy débiles, lo que dificulta en gran medida su correcta caracterización en la mayoría de técnicas. Por ello, en esta tesis, se emplea una metodología experimental capaz de aislar las moléculas de cualquier medio que perturbe dichas interacciones a la vez que permite su determinación estructural: la espectroscopía laser con resolución de masas en expansiones supersónicas. Gracias a la resolución en masa, es posible controlar el tamaño del agregado molecular de interés, permitiendo un estudio ¿a lacarta¿ de las interacciones no-covalentes en distintos ambientes. Entre los sistemas estudiados, la agregación de alcoholes aromáticos nos permite caracterizar de forma aislada la relevancia de uno de los enlaces de hidrógeno en la agregación molecular, el enlace OH···O. Otra parte de la tesis se centra en el análisis de interacciones en los monosacáridos, responsables de una infinidad de procesos de reconocimiento molecular. Por último, se estudian agregados formados por xantinas, una familia de compuestos similares a las bases de ADN, con el fin de determinar el papel de las interacciones no-covalentes en los procesos que dieron al origen de la vida268

"Se prepararon por diferentes métodos, dos compuestos polifuncionales con los siguientes grupos funcionales. Alíl, aril, carbonato y grupo ácido (-COOH), (-OH). El ácido 4-alílcarbonato benzoico (CH2=CH-CH2-OCOO-Ar-COOH, 4-ACBz) y 4-alílcarbonato fenol (CH2=CH-CH2-OCOO-Ar-OH, 4-ACPh), estos son sólidos cristalinos que se prepararon para estudiar su polimerizabilidad y reactividad con otros compuestos. Se aisló el subproducto difuncional 14PhDAC y se determinaron las condiciones de formación de su monocristal, por vez primera. Del ácido 4-alílcarbonato benzoico (4-ACBz) se derivó un nuevo carboxilato de cobre (II). Varias macromoléculas derivadas del 4-ACBz y el 4-ACPh se obtuvieron por poliadición con BPO o T-22 en presencia de comonómeros (S, DGBAC), produciendo copolímeros funcionalizados. En el caso del ácido 4-alílcarbonato, también se logró por vez primera su homopolimerización obteniéndose el Poli(4-ACBz) funcionalizado con grupos ácido. Se estudió la adsorción del dióxido de carbono, con los monómeros 4-ACPh y 4-ACBz como posibles adsorbentes. Los resultados preliminares de dicho estudio mostraron una baja capacidad de adsorción. También se describen los resultados del análisis UV del ácido, 4-ACBz y del estudio consecutivo de fluorescencia. Se determino que solo el 4-ACBz es un fluoroforo."

Here, the upconversion behaviour of Yb3+/Er3+-codoped layered Dion–Jacobson calcium-niobium perovskites was investigated. This lanthanide pair is majorly responsible for the efficient green and red anti-Stokes-like emissions in rare-earth fluorides. Layered perovskites of the composition KCa2Nb3O10 were synthesized by the ceramic method by replacing 1% per mol of Ca2+ by lanthanide ions in such a way that the Yb3+:Er3+ molar proportion varied from 2 : 1 to 20 : 1. Non-doped and four doped materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and emission spectroscopy. All materials showed similar XRD profiles, which indicated the isolation of well crystalline single phases. On the other hand, the morphologies accessed by SEM were different: microparticles with well-defined edges were replaced by particles with poorly defined edges, rounded features, and intergrowth aspect when the niobate was doped. The Raman spectra showed modifications in the bands below 200 cm−1 attributed to low-phonon-energy transitions. The doped layered niobates presented almost pure-green emission (excitation at 980 nm), which could be related to the low energy values of the vibrational levels, precluding energy loss. Additionally, the results indicated that the defects generated by the lanthanide ion isomorphic-aliovalent substitution in Ca2+ sites were mainly in the interlayer region. This coupled behaviour reduced the non-radiative decays of the upconversion centres, leading to the formation of an efficient emitting material. The spectroscopic emission data showed a two-photon major mechanism to excite the emitting levels via an energy transfer upconversion (ETU) population process. The lifetime results indicated that increasing the Yb3+ concentration did not lead to non-radiative decay paths. The high efficiency and the versatility of the layered niobate hosts can provide new insights into the design of efficient morphology-controlled materials.

Altres ajuts: CERCA Programme/Generalitat de Catalunya Aquest article té una correcció a 10.1039/d0sc90189j The spatiotemporal control of cellular dynamic processes has great fundamental interest but lacks versatile molecular tools. Dynamin is a key protein in endocytosis and an appealing target to manipulate cell trafficking using patterns of light. We have developed the first photoswitchable small-molecule inhibitors of endocytosis (dynazos), by a stepwise design of the photochromic and pharmacological properties of dynasore, a dynamin inhibitor. We have characterized their photochromism with UV-visible and transient absorption spectroscopy and their biological activity using fluorescence microscopies and flow cytometry. Dynazos are water-soluble, cell permeable, and photostable, and enable fast, single-wavelength photoswitchable inhibition of clathrin-mediated endocytosis at micromolar concentration.

Esta tesis recoge el trabajo de doctorado realizado en el Departamento de Química Física y Química Inorgánica de la Universidad de Valladolid entre septiembre de 2010 y agosto de 2014. Asimismo, y con el fin de obtener la mención de Tesis de Doctorado Internacional, la memoria recoge los trabajos realizados en varias estancias científicas internacionales, en particular en la Università di Bologna. La investigación llevada a cabo durante esta tesis doctoral ha comprendido el estudio teórico y experimental de diferentes unidades estructurales que juegan papeles importantes como bloques constructivos de diversos compuestos bioquímicos de relevancia, empleando técnicas de Química computacional y Espectroscopía de rotación. Asimismo, se han llevado a cabo estudios de varios agregados débilmente enlazados generados en chorros supersónicos. De esta manera se han analizado tanto los factores intramoleculares responsables de las estructuras moleculares de cada monómero, como las interacciones de carácter intermoleculares que se ponen en juego en el caso de los agregados (en particular, enlaces de hidrógeno e interacciones dispersivas). Se han estudiado tres familias de moléculas diferentes: tropanos, aminoésteres y decanos bicíclicos. A la primera familia molecular pertenece la escopina y la pseudopeletierina, que tienen en común el azabiciclo de tropano que aparece en muchas moléculas de interés farmacológico. Al igual que en estudios previos llevados a cabo en nuestro grupo como la tropinona y la escopolina, para ambas moléculas se encontró que las estructuras estables eran las asociadas a configuraciones piperidínicas tipo silla, con el grupo metilamino en configuraciones axial o ecuatorial., Departamento de Química Física y Química Inorgánica

[EN] In this final degree thesis a study about the energy barriers and the energy level alignments at the interface of gold contacts and a P3HT: PCBM bulk heterojunction will be presented for the first time. To do this, we will use a solid state spectroscopy method called “in-device molecular spectroscopy (i- MOS)”. We will present the fabrication procedure of the devices used in i - MOS, the hot - electron transistors. After that, we will do a comparative study of the results obtained with the bulk heterojunction of P3HT:PCBM and the results using PCBM alone. We were able to observe the lowest unoccupied molecular level (LUMO) of PCBM and an extra level for P3HT:PCBM. Finally, we will consider the next steps that could be taken in order to keep optimizing the devices made with organic materials. [ES] En esta tesis de fin de grado presentamos el primer estudio sobre el alineamiento energético en las interfaces entre contactos de oro y una heterounión de P3HT:PCBM. Para hacer esto, nos valdremos de un método espectroscópico denominado “in device molecular spectroscopy (i - MOS)”. Se presentará el método de fabricación de los dispositivos con los que realizaremos la espectroscopía, transistores de electrones calientes. Seguidamente, se realizará un análisis de los resultados obtenidos con la heterounión P3HT:PCBM y los compararemos con los resultados obtenidos con PCBM, en los que observaremos el primer nivel molecular del PCBM y el un segundo nivel en el caso de P3HT:PCBM. Finalmente, se comentarán los posibles pasos futuros a seguir para continuar con la optimización de los dispositivos hechos a base de materiales orgánicos. [EUS] Gradu amaierako lan honetan urre - kontaktuen eta P3HT:PCBM heteronioaren arteko alineamendu energetikoen lehen azterketa erakusten dugu. Honetarako "in device molecular spectroscopy (i - MOS)" izeneko espektroskopia metodo bat erabiliko dugu. Espektroskopia egiteko erabiliko diren gailuen, elektroi beroetako transistoreen, fabrikazioa ere erakutsiko da. Ondoren P3HT:PCBM-arekin lortutako datuen analisi bat egingo da eta PCBMarekin lortutako emaitzekin konparatuko dira. Azkenik gailu hauen optimizaziorako etorkizunean egin liratekeen pausoak kontsideratuko ditugu.

373 p. Uno de los mayores problemas a los que se enfrenta la comunidad científica en la actualidad es la necesidad de cambiar las fuentes de energía actuales por otras renovables, seguras, baratas y respetuosas con el medio ambiente. Con este fin, múltiples materiales han sido propuestos. Entre ellos, los dirradicales forman un tipo prometedor debido a sus propiedades físicas, fundamentalmente la pequeña distancia energética que hay entre el singlete y el triplete y la capacidad que tienen de absorber en la región del visible. Estas dos características convierten a los dirradicales en candidatos perfectos para experimentar ¿fisión de singlete¿, un mecanismo por el cual un solo fotón sería capaz de excitar a dos moléculas desde su estado fundamental al primer triplete excitado. Este proceso puede ser vital en la tecnología fotovoltaica para aumentar la eficiencia de las celdas solares.Un tipo concreto de dirradicales son aquellos que contienen dos grupos carbonilo, formando lo que se conoce como quinonas. Estas moléculas merecen ser estudiadas con detalle por los altos potenciales de reducción que proporcionan, y eso puede ser aprovechado para diseñar dispositivos de almacenamiento de energía más eficientes, baratos y respetuosos con el medio que las tradicionales baterías basadas en materiales inorgánicos como LiCoO4.Actualmente, aunque la comunidad científica ya está usando dirradicales para diseñar materiales adecuados para la captación y el almacenamiento de energía, no existe un conocimiento completo sobre muchas de las propiedades de este tipo de moléculas. Esto ocurre fundamentalmente por la dificultad que presentan para investigarlos experimentalmente debido a su inestabilidad intrínseca. Por tanto, la química teórica puede proporcionar datos valiosos para desentrañar la estructura de los dirradicales así como los mecanismos en los que están envueltos. De esa manera, esta tesis se suma al esfuerzo computacional dedicado a estudiar los dirradicales, siguiendo dos líneas principales: i) analizar los efectos que tienen en el carácter dirradical varios tipos de modificaciones estructurales tales como la introducción de heteroátomos, sustituyentes, modificación en el número y tamaño de anillos aromáticos, etc¿ ii) La búsqueda y caracterización sistemática de dirradicales, dándole particular preponderancia a aquellos que pueden ser fácilmente sintetizadas. En ambos casos, el carácter diradical se relacionará fundamentalmente con: i) las propiedades electroquímicas de cada molécula, por lo que se proporcionan datos como potenciales de reducción y oxidación, afinidades electrónicas, densidad de energía, etc ii) Los estados excitados de cada molécula, necesarios para estimar la idoneidad de cada molécula para que experimente fisión de singlete. Polymat

El rápido avance en la tecnología de fuentes de radiación y la ingeniería a nivel nanométrico van de la mano con exhaustivos análisis numéricos y analíticos, como el llevado a cabo en este proyecto, que nos permiten comprender la magnitud y complejidad de la espectroscopia molecular y su dinámica a temperaturas muy bajas (T~ μK). La presencia de radiación permite proponer esquemas de control cuántico sobre los diversos grados de libertad internos de las moléculas (estados hiperfinos, rotacionales, vibracionales). Hemos analizado aquí la dinámica de dos y tres estados electrónicos acoplados, en los cuales una gran cantidad de niveles El rápido avance en la tecnología de fuentes de radiación y la ingeniería a nivel nanométrico van de la mano con exhaustivos análisis numéricos y analíticos, como el llevado a cabo en este proyecto, que nos permiten comprender la magnitud y complejidad de la espectroscopia molecular y su dinámica a temperaturas muy bajas (T~ μK). La presencia de radiación permite proponer esquemas de control cuántico sobre los diversos grados de libertad internos de las moléculas (estados hiperfinos, rotacionales, vibracionales). Hemos analizado aquí la dinámica de dos y tres estados electrónicos acoplados, en los cuales una gran cantidad de niveles.

Esta tesis trata sobre la interacción entre las excitaciones moleculares, los plasmones y la radiación electromagnética, en un amplio abanico de situaciones que incluyen la interacción entre vibraciones moleculares y radiación infrarroja, así como la excitación y emisión de transiciones electrónicas en moléculas colorantes, en el contexto de la espectroscopia infrarroja aumentada por superficies (SEIRS), la fluorescencia aumentada por superficies (SEF) y la dispersión Raman aumentada por superficies (SERS). Para describir la interacción luz-materia se desarrollan tanto herramientas clásicas como la teoría cuántica. Algunos resultados de esta tesis, tales como la optimización de la señal producida en la espectroscopia infrarroja aumentada por superficie, tienen importancia práctica directa, otros resultados apuntan a aspectos más fundamentes de la interacción entre luz y materia. Los detalles de la compleja dinámica de las vibraciones moleculares bajo estimulación óptica, o la dinámica de la emisión de luz involucrando los estados híbridos de luz y materia, es decir, los polaritones, pueden servir como claros ejemplos de este último aspecto. Los resultados de esta tesis aspiran a servir como inspiración de futura investigación teórica y experimental adicional sobre los fenómenos en ella descritos.

Pyrazoline are widely being studied due to their potential applications in chemical field. Herein, five pyrazolines compounds were synthesized and characterized spectroscopically using nuclear magnetic resonance techniques (1H NMR &13C NMR) to determine the structures of molecules along-with UV–Visible and infrared (FT-IR) studies for additional spectroscopic support in characterization of entitle synthesized molecules. Unit cells, specific space groups, bond lengths, bond angles and hydrogen bonding interactions were determined by the x-ray diffraction studies. Further, computational study of compounds with B3LYP/6–311 + G(d,p) level were carried out to explore optimized geometry, spectroscopic data for FT-IR, frontier molecular orbitals (FMOs) and non-linear optical (NLO) parameters. While, UV–Vis spectral were performed by TD-DFT/B3LYP/6–311 + G(d,p) level. The experimental results of spectroscopic and single crystal studies were compared and found in good agreement with the computational. The global reactivity parameters have been calculated with the help of the energy of FMOs. The order for the total first and second order hyperpolarizabilities of 1–5 is found in the following orders: 1 > 4 > 3 > 5 > 2 and 1 > 4 > 5 > 2 > 3 respectively. Overall, greater NLO response than urea molecule prove that investigated molecules are excellent candidate for NLO applications.

Tesis de maestría en Ciencias, especialidad en física Infrared (IR) thermography has been utilized in the last decades for the detection of many diseases. With the growth of nanotechnology as also grown the investigation of the interactions between electromagnetic radiation and metallic nanoparticles and its heat transfer property. Such property is often used in medicine as a hyperthermia treatment for cancer. Due the importance of the heated nanoparticle applications it is a need to have a system that can monitor, recollect, process, and analyze data information coming from heated bodies. Being so, the general objective of this work is the development of an IR thermography based method to study thermal effects on surfaces. This works presents a new improved method of monitoring surface temperature changes by dynamic IR thermography. The method is based on the careful analysis of IR image sequences that allows one to select areas with significant temperature variation and evaluate temporal behavior of the surface temperature. A set of codes was written in MATLAB software to analyze the superficial changes in temperature for systems that present a volumetric or superficial heating process. To test the method, the experimental study on the photothermal effect in a gold hydrosol containing 0.3 mg/mL hollow GNPs was performed. A simple set up was designed to heat the hydrosol by laser light and monitor the hydrosol surface temperature by IR camera. It was shown that the surface temperature under the laser beam gradually increases and reaches a saturation level. The surface temperature distribution exhibit the concentric structure with the maximal temperature in the beam center. After the laser was turned off, the temperature returned to equilibrium with the area outside of the beam in about ten seconds. Numerical simulations of the experiment with the COMSOL Multiphysics Heat Transfer module were used to reproduce the measured surface temperatures and estimate the heat transfer coefficient at the hydrosol surface and photothermal conversion efficiency, the parameters that would be difficult to find byother methods. In conclusion, this work presents a new improved method for the data acquisition and data analysis based on dynamic IR thermography. This method is not limited to colloids with nanoparticles, but it can be applied for any system whose superficial temperature is change under an external stimulation. Despite the IR thermography measures only a surface temperature, it is possible, combining the precise surface temperature detection and results of numerical simulations with an adequate model, to estimate the volumetric temperature and determine 3D heat delivery during the hyperthermia procedure. Universidad de Sonora. División de Ciencias Exactas y Naturales. Departamento de Investigación en Física 2018

Agradecimentos: Defense Advanced Research Projects Agency (DARPA); National Institute of Standards and Technology (NIST); National Science Foundation (NSF) (1708743); Air Force Office of Scientific Research (AFOSR) (FA9550-16-1-0016) Abstract: Spectroscopy in the molecular fingerprint spectral region (6.7-20 mu m) yields critical information on material structure for physical, chemical, and biological sciences. Despite decades of interest and effort, this portion of the electromagnetic spectrum remains challenging to cover with conventional laser technologies. In this paper, we present a simple and robust method for generating super-octave, optical frequency combs in the fingerprint region through intra-pulse difference frequency generation in an orientation-patterned gallium phosphide crystal. The attainable brightness from this tabletop source reaches the same level achievable by infrared synchrotron radiation with a bandwidth spanning from 4 to 12 mu m. We demonstrate the utility of this unique coherent light source for high-precision, dual-frequencycomb spectroscopy of methanol and ethanol vapor. These results highlight the potential of laser frequency combs for a wide range of infrared molecular sensing applications from basic molecular spectroscopy to nanoscopic imaging fechado

8 pags.; 4 figs.; 3 tabs.; 7th IDMRCS: Relaxation in Complex Systems, © 2014 Elsevier B.V. All rights reserved. The thermal conductivity of CBrnCl4 -n,(n = 0,1,2) and 2-adamantanone (C10H14O) crystals which exhibit substitutional disorder has been measured for temperatures between 2 K and 150 K. Such temperatures comprise signatures of dynamical processes involving the site occupancy of the chlorine and bromine atoms for CBrnCl4 -n,(n = 0,1,2) and the oxygen atom for (C10H14O), as it has been revealed by both, calorimetry and spectroscopic techniques. The data analysis is carried out in terms of several phonon scattering channels contributing to a resistive relaxation rate which can be represented by two contributions due to propagating phonons whose mean-free path exceeds half the phonon wavelength as well as a term attributed to localized short wavelength modes. The implications of the present findings for studies pertaining to glassy dynamics are briefly discussed., This work is supported by the Spanish Ministry of Science and Innovation (grant no. FIS2011-24439), the Catalonia Government (grant no. 2009SGR-1251). The authors acknowledge the support from the National Academy of Science of Ukraine in the frame of the joint Ukrainian– Russian Project (agreement no. 10-2012) on the subject “Metastable states of simple condensed systems”. One of us A.I. K. thanks the Spanish Ministry of Education (grant SAB2011-0070) for an invited position at the Universitat Politècnica de Catalunya.

Made available in DSpace on 2018-12-11T17:13:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-09-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Complexes of the type cis-[PdX2(imzt)(PPh3)] {imzt = imidazolidine-2-thione; PPh3 = triphenylphosphine; X = Cl (1), Br (2), I (3), SCN (4)} have been synthesized and characterized by elemental analyses, molar conductance, IR and 1H NMR spectroscopies. The complex 1·MeOH was obtained from the reaction of [PdCl2(CH3CN)2], imidazolidine-2-thione and triphenylphosphine in CHCl3/CH3OH. Complexes 2·MeOH, 3 and 4 were prepared by metathesis of the chlorido ligands in 1 with bromide, iodide and thiocyanate, respectively. Elemental analyses showed good agreement with the expected mononuclear compositions, while the molar conductivities of the complexes in DMF were consistent with their nonelectrolytic nature. NMR spectra confirmed coordination of the imidazolidine-2-thione and triphenylphosphine ligands. Single-crystal X-ray diffraction determination of 1·CH3OH showed that the coordination geometry around PdII is nearly square planar, with the chlorido ligands in a cis configuration. All four complexes have been tested in vitro by XTT assay for their cytotoxicity against human glioblastoma cell line (U87MG). The binding of 1 with guanosine was studied by 1H NMR spectroscopy, revealing that the coordination takes place via N7. Departamento de Química Geral e Inorgânica Instituto de Química de Araraquara UNESP – Univ Estadual Paulista, P.O. Box 355 Departamento de Biologia Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, USP Av. Bandeirantes 3900 Departamento de Química Universidade Federal de São Carlos Instituto de Química UNIFAL - MG - Univ Federal de Alfenas Instituto de Química de São Carlos Universidade de São Paulo, Avenida Trabalhador São-carlense, 400 Departamento de Química Geral e Inorgânica Instituto de Química de Araraquara UNESP – Univ Estadual Paulista, P.O. Box 355 FAPESP: 2009/54011-8 FAPESP: 2016/17711­5

In this work of thesis we describe the design, development and characterization of a new diagnosis instrument intended to perform systematic campaigns of simultaneous measurement of the spectrum and polarization degree of the light emitted by transient luminous events (TLEs) as a ground support to space missions ASIM (ESA) and TARANIS (CNES) to be launched by early and late 2018, respectively. The GRASSP instrument (GRAnada Sprite Spectrograph and Polarimeter) includes the rst medium{high spectrograph specifically designed for the analysis of air plasmas generated by TLEs. All versions of GRASSP have been developed and characterized by our group at the Institute of Astrophysics of Andalusia (IAA, Granada, Spain) and the Institute of Matter Structure (IEM, Madrid, Spain) laboratories, both dependencies of the National Research Council of Spain (CSIC)., We have developed four di erent versions of GRASSP to date. We installed the rst (2012 { 2014) and second (2014 { 2015) versions of GRASSP at the Spanish{German Astronomic Center (CAHA) in Calar Alto, Almer a, Spain. Both worked in an autonomous way, without the support of an operator. Every sunset, the system powered on automatically, took the calibration images, opened the blinds of the system and aimed the spectrograph to the region of the sky where a TLE was more probable to appear. This could be done thanks to an aiming algorithm we developed that queried the databases of the Spanish Weather Agency (AEMET) in real-time and calculated the coordinates of the closest storm. When the system detected a change of the brightness level in the sky, an audio trigger system launched the simultaneous recording of both eld image and spectral image to store them in a data repository. This way we could discern the origin of the recorded spectra. Every sunrise, after the observation night, the algorithm closed blinds and switched o all the GRASSP subsystems. From this location we obtained the rst TLE images recorded with GRASSP, we recorded several spectra from lightning optical emissions dispersed on clouds and we had the chance of recording a meteoroid spectrum while it passed in front of GRASSP. Unfortunately, from this location we did not record any TLE spectra because of the remoteness of the storms, that occur most frequently in Spain in the Ebro Delta valley., Hence we decided to relocate our spectrograph in a new and compact version of GRASSP. We installed GRASSP versions three (2015 { 2016) and four (2016 { now) in Castellgal , Barcelona, Spain. This last compact version is currently located within the stormiest region of north-eastern Spain, with a eld of view of almost 360 degrees, and it is manually aimed by an experienced colleague (Oscar Van der Velde, from Polytechnic University of Catalonia). Since the installation of the third version of GRASSP we have recorded up to 44 medium{ high resolution TLE spectra, that allowed us to quantify, for the rst time, the (rotational) temperature of gas surrounding TLEs. It can be done through the spectral tting of the recorded spectrum to synthetic spectrum that we have modelled, thanks to the high resolution of our spectrograph (0.235 nm) that allows us to t the rovibrational bands of the nitrogen molecule. This way we can understand TLEs as natural probes of the air temperature in the Earth mesosphere. It is the rst time that systematic campaigns of spectroscopic measurements of TLEs with such high resolution have been developed (the best spectral resolution to date intended to sporadically analyze TLEs spectra is 3 nm), with the goal of feeding a database to statistically characterize the TLEs from a spectroscopic point of view in a near future. The GRASSP polarimeter is currently in calibration stage within our laboratories. It is intended to be operative from summer 2017., This work has been made possible with the nancial assistance of the Spanish Ministry of Science and Innovation, MINECO (previously MICINN) under projects AYA2009-14027-C05-02, AYA2011-29936-546-C05-02, ESP2013- 48032-C5-5-R, FIS2014-61774-EXP, ESP2015-69909-C5-2-R and FQM{5965; the European Science Foundation (ESF) Research Networking Programmes under project 09-RNP-101 and the EU through the FEDER program.

521 p. DNA and proteins are involved in biological processes which make possible life. On the one hand, the four DNA bases constitute the alphabet of life. Their normal appearance includes stacked Watson-Crick pairs in order to form DNA strands, reinforced by the existence of the sugar backbone. However, the appearance of unusual structures, such as Hoogsteen pairs, triplexes and quadruplexes, raises the question of which are the intrinsic preferences of the DNA aggregation. On the other hand, proteins are chains of amino acids, whose interactions with DNA strands are the basis of the nucleosome formation. The mechanism which guides the nucleosome formation is still bewildering. The first goal of this thesis is the characterization of the non-covalent interactions in biological species and their aggregates by a combination of DFT calculations and Non-Covalent Interaction approach. The second goal is the elaboration of a reductionist model applying theoretical calculations, based in amino acid-DNA base interactions, in order to explain the leading mechanism of the histone-DNA formation. Finally, the third goal is the study of the intrinsic preferences of the DNA base self-aggregation process, analyzing the tautomerical landscape of the DNA bases, focusing on the competition between hydrogen bond and dispersive contributions. A combination of theoretical calculations and spectroscopic techniques has been used to understand the self-aggregation of purines (guanine) and pyrimidines (cytosine) in gas phase.

Viologen–tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (kobs < 1012 s–1) and twisted (kobs ∼ 1010 s–1) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push–pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V•+).

The ground and the low lying electronic states of structures on the 1,3[H, C, As] potential energy surfaces were investigated with the highly correlated theoretical approaches CCSD(T), CCSD(T)-F12b, and CASSCF/MRCI along with the series of correlation consistent (aug-cc-pVnZ, n = D, T, Q, 5) basis sets. Energetic and spectroscopic parameters were obtained at the complete basis set limit, and the effect of core-valence correlation on these properties evaluated. Fundamental frequencies were also computed with the variational configuration interaction (VCI) approach. Heats of formation at 0 and 298.15 K were estimated for HCAs and CH, AsH, CAs, and HCAs, as well as the calculation of ionization potentials for HCAs. Comparisons of the present results with literature ones for the systems HCN/HNC, HCP/HPC highlight similarities and differences among these systems. Altogether, this investigation provides a very reliable characterization of the species on the surfaces and should guide future experimental studies on these systems.

232 p., In this work different versatile photoactive hybrid materials with interesting features for optics and biomedicine are achieved and exhaustively characterized. Firstly, by means of the occlusion of different fluorescent dyes, by the crystallization inclusion method, into several 1D-channeled magnesium aluminophosphate (MgAPO) hosts (with different sized and shaped pores), optically dense fluorescent hybrid materials which show highly anisotropic response to linearly polarized light are obtained. Depending on the dye embedded within the selected MgAPO framework, interesting applications have been attained, such as one-directional artificial photonic antenna systems covering the whole UV-Visible spectral range, Second Harmonic Generators under NIR radiation, optically switchable hybrid systems and white light emitters. White light emission is also obtained from the luminescence that arises from embedding simultaneously different small aromatic molecules into a Metal Organic Framework (MOF), named [Zn2(bdc)2(dpNDI)]n, which contains a photoactive naphtalemediimide as organic pillar. The incorporation of halide-substituted aromatic molecules into this MOF also promotes phosphorescence at room temperature. Finally, the attachment of a BODIPY chromophore to a cyclometalated Ir(III) metallic centre results in the achievement of efficient photosensitizers for singlet oxygen generation upon visible excitation light. Moreover, these hybrid compounds also show fluorescence emission, thus, they are interesting for bioimaging as well, and as a consequence, extensible to their use in theragnosis.

Neste trabalho foram desenvolvidas metodologias de análise de cocaína mediante as técnicas de imagem digitais, espectroscopia no infravermelho (FTIR), ambas associadas com quimiometria, e cromatografia a líquido com detector de arranjo de diodo (LC-DAD) otimizada por planejamento experimental. O objetivo do trabalho foi desenvolver métodos analíticos capazes de identificar um material desconhecido como cocaína, realizar uma triagem para obtenção do perfil químico e, por fim, quantificar os componentes da cocaína droga. Para isto, foram utilizados métodos de análise multivariada não supervisionada, como a análise hierárquica por agrupamentos (HCA) e a análise por componentes principais (PCA), e supervisionada, como a análise discriminante por mínimos quadrados parciais (PLS-DA), análise discriminante por máquinas de vetores de suporte (SVM-DA), entre outros, juntamente com métodos instrumentais de análise. Para o estudo de identificação de amostra desconhecida, foram preparadas misturas de cocaína e seus adulterantes, as quais foram avaliadas pelo teste de Scott associado com imagens digitais. Para triagem e obtenção do perfil químico, foi realizado um planejamento de misturas da cocaína e seus principais adulterantes. Estas misturas foram analisadas por infravermelho e seus perfis comparados, através da análise multivariada dos espectros de infravermelho, com amostras apreendidas pela Polícia Federal (PF) no estado do Rio Grande do Sul Para quantificação de cocaína e 6 adulterantes, foram analisadas amostras de cocaína mediante LC-DAD com as condições otimizadas por planejamento experimental Doehlert e seus perfis comparados com as amostras dos demais estados do Brasil. Um dos principais resultados deste trabalho, foi aumentar a especificidade do teste de Scott pela associação do mesmo a análise multivariada. Por exemplo, a lidocaína, que também resultava em positivo para o teste, pode ser discriminada da cocaína. Foi possível também obter um perfil de adulteração da droga, a forma da cocaína (base ou sal) com alta acurácia e compará-la com a droga proveniente de outras apreensões através de FTIR na etapa de triagem. Por fim, na etapa de quantificação por LC-DAD, as figuras de mérito da metodologia foram avaliadas, sendo o método considerado apropriado para seu objetivo. O perfil da cocaína apreendida pela PF no estado do Rio Grande do Sul é diferente do perfil da cocaína traficada em outros estados do país em relação a pureza, mas similar em relação à adulteração. In this work, methodologies were developed for cocaine analysis using digital image techniques, infrared spectroscopy (FTIR), both associated with chemometrics, and liquid chromatography with diode array detector (LC-DAD) optimized by experimental design. The aim of this work was to develop an analytical methodology capable of identifying unknown material as cocaine, performing a screening to obtain the chemical profile and, finally, quantifying the cocaine drug components. For this, we used non-supervised multivariate analysis methods such as hierarchical cluster analysis (HCA) and principal component analysis (PCA), and supervised methods, such as partial least squares discriminant analysis (PLS-DA), support vector machines discriminant analysis (SVM-DA), among others. For the unknown sample identification study, a mixture design of cocaine and its adulterants was prepared for analysis by the Scott test associated with digital image analysis. In the screening step, it was performed a mix of cocaine and its main adulterants and their profiles were evaluated, using multivariate analysis of the infrared spectra, with samples seized by the Federal Police (PF) in the state of Rio Grande do Sul For the quantification of cocaine and 6 adulterants, cocaine samples seized by PF were evaluated using LC-DAD with the conditions optimized by Doehlert experimental design and compared their profiles with other states of Brazil. As main results of this work, it was possible to increase the specificity of the Scott test with the association with multivariate analysis: lidocaine that also resulted in positive for the test could be discriminated. In the screening stage, through FTIR, it was possible to obtain an adulteration profile of the drug, the form of cocaine with high accuracy and a comparison with other seizures. Finally, in the quantification step, the parameters of merit of the methodology were evaluated, being considered appropriate for its objective. The profile of cocaine seized by PF in the state of Rio Grande do Sul was different from the other states of Brazil in relation to purity, but a similar profile of adulteration.

332 p. En el presente proyecto de tesis un nuevo modus operandi es descrito, siendo este aplicable a estudios de propiedades químicas fundamentales y la generación de conocimiento base. Estos conocimientos fundamentales son en numerosas ocasiones el sustento para la realización de proyectos de investigación más aplicados. En concreto la tesis se centra en la determinación estructural y el análisis de interacciones no-covalentes. Estas fuerzas, difícilmente observables con la mayoría de técnicas, son las responsables de controlar una infinidad de características, empezando por la tremenda selectividad de las reacciones bioquímicas hasta ser en parte responsables de las propiedades de algunos polímeros, etc. La técnica experimental utilizada para la determinación estructural es la espectroscopia laser con resolución de masas, esta técnica permite el estudio de sistemas aislados generados a la carta, de este modo es posible el análisis de una amplia gama de agregados obteniendo de manera selectiva la contribución de cualquier pequeña modificación. Entre los sistemas estudiados se encuentran: La Glucosa (sistema modelo de moléculas flexible), un péptido (Treonina-Alanina-Alanina) y un polímero con base de antraceno (sistema modelo para el estudio de foldameros) y Los agregados de teobromina (como modelo para las etapas iniciales en procesos de nucleación). Finalizando con una amalgama de resultados experimentales que mezclan estas tres tipos de metodologías. Además se han implementado avances en el cálculo teórico y en diseño del sistema experimental.

Agradecimentos: The authors thank Nathan Newbury and Ian Coddington of NIST for discussions, and Dan Hickstein and Kevin Cossel of NIST for useful feedback on the manuscript. We acknowledge the support of NIST (including the Greenhouse Gas and Climate Science Measurement Program), the DARPA SCOUT program, and CNPq (Brazil). This work is a contribution of the US Government and is not subject to copyright in the United States. The mentioning of company and product names is for technical communication only and does not constitute an endorsement by NIST Abstract: A tunable mid-infrared frequency comb was created via difference frequency generation. Pulses between 1 and 1.5 µm were mixed to generate light ranging from 2.6 to 5.2 µm. Two such combs were heterodyned at 5 µm to show their coherence and potential for spectroscopy. The properties of the comb were modeled using numerical simulation, which confirmed the observed bandwidths CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQ Fechado

A thesis submitted in partial fulfillment for the degree of Doctor of Philosophy in the Faculty of Physics and Materials Science., Reversibly photoswitchable uorescent proteins (RSFPs) are genetically engineered proteins that can be switched by light absorption between a uorescent ON state and a dark OFF state. Among other applications they allow to increase the resolution beyond the difraction limit in cell imaging by fluorescence microscopy. RSFPs have extended the possibilities of fluorescence microscopy and other biotechnological tools, but the development of their properties is still far from being rationally designed. Thus, there might be much room for improvement if we manage to understand the switching mechanisms. The switching mechanisms in several negative RSFPs is being elucidated but still under debate. In this thesis I extend the theoretical knowledge about the photoswitching of negative RSFPs by studying the excited-state potential energy surface of both the ON- and the OFF-state. I compare three RSFPs, namely IrisFP, Dronpa and a fast switching single mutant of Dronpa called Dronpa2 to search for the origin of their different switching quantum yields in the ON-state. For the OFF-state, the results of the combined quantum mechanics-molecular mechanics (QM/MM) calculations show that chromophore photoisomerization happens in its neutral form and is followed by ground state deprotonation. This is in agreement with a very recent ultrafast absorption spectroscopy study for IrisFP, and studies on Dronpa and other negative RSFPs. Although the experimental results in both proteins show the same steps, I found that they have different processes at the atomic level due to structural and electrostatical differences, but leading to the same intermediates. This is in contrast to the ON-state where I get the same picture for the three proteins studied, identifying the conical intersection that quenches the uorescence and controls the photoswitching quantum yield. The major difference between the three proteins in terms of fluorescence and photoswitching characteristics comes from the different sterical environment produced by the residue 159, which is a methionine in different isomers in IrisFP and Dronpa and a smaller threonine that allows a faster isomerization of the chromophore in Dronpa2.

The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long-lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the 1Lb, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240ps. We have also simulated the time evolution of the 2D-UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25000 and 38000cm-1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D-UV spectroscopy to disentangle the photophysics of multichromophoric systems We acknowledge the participation of the late Luis Serrano- Andrés in the first stage of this work. L.B. and A.V. acknowledge financial support from the Spanish Ministry of Economy (CTQ2011-26573, CTQ2015-69363-P) and the Generalitat de Catalunya (2014SGR-1202) and the use of computer time at the Consorci de Serveis Universitaris de Catalunya. Q.L. acknowledges the National Natural Science Foundation of China (21303007). M.G. acknowledges support by the European Research Council Advanced Grant STRATUS (ERC-2011-AdG No.291198) and the Agence Nationale de la Recherche for the 2015 project FEMTO-2DNA (Spectroscopie 2DUV: un nouvel outil pour l’étude de biomolécules, ANR-15-CE29-0010). D.R.-S. acknowledges support from the Generalitat Valenciana (GV2015-057) and the Spanish Ministry of Economy (project CTQ2014-58624-P and grant JCI-2012-13431). S.M gratefully acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences division, office of Basic Energy Sciences, U.S. Department of Energy, and the National Science Foundation (grant CHE-1361516)

133 p. + anexos, La presente tesis doctoral se centra en el análisis de la influencia de la estructura molecular en laspropiedades fotofísicas de los cromóforos conocidos como BODIPYs. Se pretende, de esta forma,relacionar las propiedades espectroscópicas con el comportamiento de los colorantes como mediosactivos de láseres sintonizables principalmente, y también como sondas moleculares para monitorizar laspropiedades fisicoquímicas del medio que les rodea.El patrón de sustitución del BODIPY ha permitido modular y optimizar sus propiedadesespectroscópicas. De hecho, tanto la posición cromofórica en la que se incorpore el sustituyente como sucarácter dador/aceptor de electrones determina la respuesta fluorescente del colorante. ,Así, la modificación controlada de la estructura molecular básica del BODIPY ha permitido no sólooptimizar la eficiencia en la región verde/amarilla del espectro visible (funcionalización del puente deboro), sino también extenderla de forma modulable hacia el extremo azul (heteroátomos en mesa) oalternativamente a la región roja/NIR (extensión del sistema re deslocalizado). Como resultado se handesarrollado nuevos colorantes láser BODIPY cubriendo toda la región espectral visible y conprestaciones fotofísicas y láser mejoradas respecto a los colorantes comerciales existentes.Además, la funcionalización selectiva ha facilitado también promover la activación de nuevos procesosfotofísicos. La inducción de procesos de transferencia de carga por medio de la aminación o la nitración,permite emplear dichos fluoróforos como sondas fluorescentes de polaridad. Por otra parte, los procesosde transferencia de energía que tienen lugar en sistemas multicromofóricos basados en estructuras deBODIPYs y cumarinás unidas covalentemente, posibilita mejorar la absorción de luz y obtener labrillante emisión del BODIPY tanto bajo excitación visible como ultravioleta.

A connection between an algebraic approach to the dynamics of triatomic molecules based on the U(2)×U(3)×U(2) Lie algebra and the traditional description in configuration space is presented. The connection is established in four steps. First, the molecular Hamiltonian is expanded in symmetrized local coordinates. Second, the Hamiltonian is transformed into an algebraic representation by introducing the realization of coordinates and momenta in terms of bosonic creation and annihilation operators of normal character. The third step is to perform a canonical transformation applied to the bosons associated with the stretching degrees of freedom in order to obtain a unified representation in a local scheme. Finally, an anharmonization procedure is applied to identify the U(2) × U(3) × U(2) dynamical algebra. The main advantage of the proposed approach is that it provides relations between the spectroscopic parameters and the molecular structure and force constants. As an application, the analysis of the vibrational excitations of CO2 in its ground electronic state is considered. In this scheme, each stretching degree of freedom is identified as an interacting Morse oscillator, with an associated U(2) dynamical algebra, and the doubly degenerate bending degree of freedom is modelled with a U(3) dynamical algebra, obtaining as a final result a reasonable set of force constants.

[ES]En relación a otros sistemas de coordenadas, el uso de CIVs para describir las vibraciones moleculares y expresar las constantes de fuerzas de moléculas poliatómicas presenta importantes ventajas, ya que con ello se consigue una más clara interpretación fisicoquímica de dichas constantes y la posibilidad de poder hacer una mejor comparación y transferencia de dichos parámetros a moléculas semejantes. Por el contrario, su uso puede presentar problemas de ambigüedad, ya que el número de CIVs a definir puede ser mayor que el de grados de libertad vibracionales de la molécula en cuestión. En la década de los 80, Kuczera presentó una primera solución a dicho problema de la ambigüedad en la aproximación armónica y desde la década de los 90 nuestro GI ha venido trabajando en su aplicación y generalización, principalmente, para el caso de moléculas ramificadas XYn. Esta tesis busca desarrollar y generalizar lo hecho hasta ahora: Proponiendo un formalismo general para el tratamiento de los campos de fuerzas moleculares anarmónicos, de una forma canónica no ambigua utilizando CIVs; Aplicándolo a los tipos de moléculas ramificadas XY3 (D3h), XY4 (Td) y XY3Z (C3V); Estudiando las posibles correlaciones entre las constantes de fuerza canónicas de estas moléculas [EN]Using VICs to describe molecular vibrations and express forces constants of polyatomic molecules has important advantages, compared with other coordinate systems, because of both a clearer physicochemical interpretation of these constants and the possibility of getting a better comparison and transfer of them among similar molecules. On the contrary, their use can present problems of ambiguity, since the number of VICs defined may be greater than the vibrational degrees of freedom of the molecule. In the 80s, Kuczera present a first solution to the problem of the ambiguity in the harmonic approximation and from the 90s our GI has been working on its implementation and generalization, mainly in the case of branched molecules XYn. This thesis aims to develop and generalize what has been done so far: - Suggesting a general formalism for treating the anharmonic molecular force fields in a canonical unambiguous way by using VICs. - Applying it to the types of branched molecules XY3 (D3h), XY4 (Td) and XY3Z (C3V). - Studying the possible correlations among the canonical force constants of these molecules. Tesis Univ. Jaén. Departamento de Química Física y Analítica, leída el 12 de febrero de 2016