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Detailed investigations of molecular collisions at the gas-surface interface provide insight into the dynamics and mechanisms of important interfacial reactions. A thorough understanding of the fundamental interactions between a gas and surface is crucial to the study of heterogeneous chemistry of atmospheric organic aerosols. In addition to changing the chemical and physical properties of the particle, reactions with oxidizing gases may alter aerosol optical properties, with implications for the regional radiation budget and climate. Molecular beams of CO₂, NO₂ and O₃ were scattered from long-chain methyl (CH₃-), hydroxyl (OH-), vinyl (H₂C=CH-) and perfluorinated (CF₃(CF₂)₈-, or F-) ω-functionalized alkanethiol self-assembled monolayers (SAMs) on gold, to explore the reaction dynamics of atmospherically important triatomics on proxies for organic aerosols. Energy exchange and thermal accommodation during the gas-surface collision, the first step of most interfacial reactions, was probed by time-of-flight techniques. The final energy distribution of the scattered molecules was measured under specular scattering conditions (θi = θf = 30°). Overall, extent of energy transfer and accommodation was found to depend on the terminal functional group of the SAM, incident energy of the triatomics, and gas-surface intermolecular forces. Reaction dynamics studies of O3 scattering from H2C=CH-SAMs revealed that oxidation of the double bond depend significantly on O₃ translational energy. Our results indicate that the room-temperature reaction follows the Langmuir-Hinshelwood mechanism, requiring accommodation prior to reaction. The measurements also show that the dynamics transition to a direct reaction for higher translational energies. Possible environmental impacts of heterogeneous reactions were probed by evaluating the change in the optical properties of laboratory-generated benzo[a]pyrene (BaP)-coated aerosols, after exposure to NO₃ and NO₂, at 532 nm and 355 nm by three aerosol analysis techniques: cavity ring-down aerosol spectroscopy (CRD-AS) at 355 nm and 532 nm, photoacoustic spectroscopy (PAS) at 532 nm, and an aerosol mass spectrometer (AMS). Heterogeneous reactions may lead to the nitration of organic-coated aerosols, which may account for atmospheric absorbance over urban areas. Developing a detailed understanding of heterogeneous reactions on atmospheric organic aerosols will help researchers to predict the fate, lifetime, and environmental impact of atmospherically important triatomics and the particles with which they collide. / Ph. D.

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<p>The study and understanding of molecular interactions is fundamentally important in today's field of life sciences and there is a demand for well designed surfaces for biosensor applications. The biosensor has to be able to detect specific molecular interactions, while non-specific binding of other substances to the sensor surface should be kept to a minimum.                                                                                                                                                                                The objective of this master´s thesis was to design sensor surfaces based on self-assembled monolayers (SAMs) and evaluate their structural characteristics as well as their performance in Biacore systems. By mixing different oligo (ethylene glycol) terminated thiol compounds in the SAMs, the density of functional groups for bimolecular attachment could be controlled.  Structural characteristics of the SAMs were studied using Ellipsometry, Contact Angle Goniometry, IRAS and XPS. Surfaces showing promising results were examined further with Surface Plasmon Resonance in Biacore instruments.<p>Mixed SAM surfaces with a tailored degree of functional COOH groups could be prepared. The surfaces showed promising characteristics in terms of stability, immobilization capacity of biomolecules, non-specific binding and kinetic assay performance, while further work needs to be dedicated to the improvement of their storage stability. In conclusion, the SAM based sensor surfaces studied in this thesis are interesting candidates for Biacore applications.</p></p>

The study and understanding of molecular interactions is fundamentally important in today's field of life sciences and there is a demand for well designed surfaces for biosensor applications. The biosensor has to be able to detect specific molecular interactions, while non-specific binding of other substances to the sensor surface should be kept to a minimum.                                                                                                                                                                                The objective of this master´s thesis was to design sensor surfaces based on self-assembled monolayers (SAMs) and evaluate their structural characteristics as well as their performance in Biacore systems. By mixing different oligo (ethylene glycol) terminated thiol compounds in the SAMs, the density of functional groups for bimolecular attachment could be controlled.  Structural characteristics of the SAMs were studied using Ellipsometry, Contact Angle Goniometry, IRAS and XPS. Surfaces showing promising results were examined further with Surface Plasmon Resonance in Biacore instruments.Mixed SAM surfaces with a tailored degree of functional COOH groups could be prepared. The surfaces showed promising characteristics in terms of stability, immobilization capacity of biomolecules, non-specific binding and kinetic assay performance, while further work needs to be dedicated to the improvement of their storage stability. In conclusion, the SAM based sensor surfaces studied in this thesis are interesting candidates for Biacore applications.

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Self-assembled monolayers (SAMs) provide well-defined and ordered films of molecules spontaneously chemisorbed on a surface. By designing molecules with desired functionalities, such molecular film can be interesting for a range of applications from molecular electronics to catalysis. Important parameters for SAM applications are the film structure and quality, which are dependent on the structure of molecular constituents, the substrate, and the self-assembly process. In this work, SAMs on Au(111) of a variety of functionalized molecules, with thiol and silane headgroups, have been studied using high-resolution X-ray photoemission spectroscopy (HRXPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, Infrared reflection absorption spectroscopy (IRRAS), contact angle measurements and Kelvin probe measurements. In particular, the effects of varying the size of the backbone, varying the headgroup, inclusion of a porphyrin tailgroup, different ways of deprotection of the headgroups, and mixed molecular layers have been investigated. The first part of thesis work is focused on SAMs of oligo(phenyleneethynylene) (OPE) derivatives. First the effect of the extent of the conjugated system on the structure of SAM was investigated. As the lateral π-system in the OPE backbone increases, molecular surface densities become lower and molecular inclinations larger. Subsequently, a bulky porphyrin tailgroup was added onto the OPE molecule. Porphyrin-functionalized OPE with several headgroups were compared and the thioacetyl anchor group was found to form a high quality SAM. In the second part of the work, the molecular orientation of thiol-derivatized tetraphenylporphyrin layers was studied. The geometry of the molecular layer and the number of linkers that bind to the gold surface depend strongly on preparation schemes, i.e. whether or not the acetyl protection groups on the thiol were removed before adsorption. Finally, mixed SAMs of a ferrocene-terminated alkanethiol and alkanethiols were studied. By diluting the ferrocene-functionalized molecules in unfunctionalized alkanethiols, the orientational order and the packing density improved. The geometrical structure and the fraction of the ferrocene-terminated molecules can be tuned by controlling the parameters in the preparation scheme.

This thesis studies the interaction between the bare Cu{311} surface with NO and NH3,individually and co-adsorbed using reflection-absorption infrared spectroscopy (RAIRS). In addition to the bare Cu{311} surface, the interaction of NO and NH3 with the various oxygen phases of the Cu{311} surface phases was also studied. Several other techniques were used in tandem to support the study, such as low energy electron diffraction (LEED) and temperature programmed desorption (TPD) experiments using mass spectrometry. The study was carried out in pursuit an understanding of the underlying mechanism of the selective catalytic reduction (SCR) of NO using NH3 in current diesel engines. The dosing of NO onto the Cu{311} surface at 100 K leads to the initial adsorption of intact NO. After an exposure threshold is reached, individual NO molecules react with another NO molecule to form (NO)2 dimers. These dimer species subsequently form N2O, leaving O(a) on the surface. Oxygen was found to be an inhibitor for the reaction, either due to the reaction in a self-poisoning process or from oxygen pre-dosing onto the Cu{311} surface. Temperature plays a minor role with regards to NO/Cu{311}, as it only affects the amount of NO on the surface along with adsorbate surface mobility. Similarly, NH3 was found to adsorb intact onto the Cu{311} surface and not to react or dissociate at 100 K. Oxygen acts as a site blocker for the adsorption, but can also stabilise NH3 to remain on the surface at higher temperatures due to electronic effects. At 300 K, it was found that both the bare and oxygen pre-covered Cu{311} surface was able to dissociate NH3 into NH2. The co-adsorption of NO and that of NH3 onto the Cu{311} surface were found to be largely independent of each other and the interaction is dominated by the displacement of NO by NH3. However, as NO adsorption on the Cu{311} surface forms O(a), it indirectly affects the adsorption of NH3 by creating an oxygen covered Cu{311} surface, which changes how NH3 adsorbs onto the surface.

Tesis por compendio / [EN] Phononic crystals are artificial materials formed by a periodic arrangement of inclusions embedded into a host medium, where each of them can be solid or fluid. By controlling the geometry and the impedance contrast of its constituent materials, one can control the dispersive properties of waves, giving rise to a huge variety of interesting and fundamental phenomena in the context of wave propagation. When a propagating wave encounters a medium with different physical properties it can be transmitted and reflected in lossless media, but also absorbed if dissipation is taken into account. These fundamental phenomena have been classically explained in the context of homogeneous media, but it has been a subject of increasing interest in the context of periodic structures in recent years as well. This thesis is devoted to the study of different effects found in sonic and phononic crystals associated with transmission, reflection and absorption of waves, as well as the development of a technique for the characterization of its dispersive properties, described by the band structure. We start discussing the control of wave propagation in transmission in conservative systems. Specifically, our interest is to show how sonic crystals can modify the spatial dispersion of propagating waves leading to control the diffractive broadening of sound beams. Making use of the spatial dispersion curves extracted from the analysis of the band structure, we first predict zero and negative diffraction of waves at frequencies close to the band-edge, resulting in collimation and focusing of sound beams in and behind a 3D sonic crystal, and later demonstrate it through experimental measurements. The focusing efficiency of a 3D sonic crystal is limited due to the strong scattering inside the crystal, characteristic of the diffraction regime. To overcome this limitation we consider axisymmetric structures working in the long wavelength regime, as a gradient index lens. In this regime, the scattering is strongly reduced and, in an axisymmetric configuration, the symmetry matching with acoustic sources radiating sound beams increase its efficiency dramatically. Moreover, the homogenization theory can be used to model the structure as an effective medium with effective physical properties, allowing the study of the wave front profile in terms of refraction. We will show the model, design and characterization of an efficient focusing device based on these concepts. Consider now a periodic structure in which one of the parameters of the lattice, such as the lattice constant or the filling fraction, gradually changes along the propagation direction. Chirped crystals represent this concept and are used here to demonstrate a novel mechanism of sound wave enhancement based on a phenomenon known as "soft" reflection. The enhancement is related to a progressive slowing down of the wave as it propagates along the material, which is associated with the group velocity of the local dispersion relation at the planes of the crystal. A model based on the coupled mode theory is proposed to predict and interpret this effect. Two different phenomena are observed here when dealing with dissipation in periodic structures. On one hand, when considering the propagation of in-plane sound waves in a periodic array of absorbing layers, an anomalous decrease in the absorption, combined with a simultaneous increase of reflection and transmission at Bragg frequencies is observed, in contrast to the usual decrease of transmission, characteristic in conservative periodic systems at these frequencies. For a similar layered media, backed now by a rigid reflector, out-of-plane waves impinging the structure from a homogeneous medium will increase dramatically the interaction strength. In other words, the time delay of sound waves inside the periodic system will be considerably increased resulting in an enhanced absorption, for a broadband spectral range. / [ES] Los cristales fonónicos son materiales artificiales formados por una disposición periódica de inclusiones en un medio, pudiendo ambos ser de carácter sólido o fluido. Controlando la geometría y el contraste de impedancias entre los materiales constituyentes se pueden controlar las propiedades dispersivas de las ondas. Cuando una onda propagante se encuentra un medio con diferentes propiedades físicas puede ser transmitida y reflejada, en medios sin pérdidas, pero también absorbida, si la disipación es tenida en cuenta. La presente tesis está dedicada al estudio de diferentes efectos presentes en cristales sónicos y fonónicos relacionados con la transmisión, reflexión y absorción de ondas, así como el desarrollo de una técnica para la caracterización de sus propiedades dispersivas, descritas por la estructura de bandas. En primer lugar, se estudia el control de la propagación de ondas en transmisión en sistemas conservativos. Específicamente, nuestro interés se centra en mostrar cómo los cristales sónicos son capaces de modificar la dispersión espacial de las ondas propagantes, dando lugar al control del ensanchamiento de haces de sonido. Haciendo uso de las curvas de dispersión espacial extraídas del análisis de la estructura de bandas, se predice primero la difracción nula y negativa de ondas a frecuencias cercanas al borde de la banda, resultando en la colimación y focalización de haces acústicos en el interior y detrás de un cristal sónico 3D, y posteriormente se demuestra mediante medidas experimentales. La eficiencia de focalización de un cristal sónico 3D está limitada debido a las múltiples reflexiones existentes en el interior del cristal. Para superar esta limitación se consideran estructuras axisimétricas trabajando en el régimen de longitud de onda larga, como lentes de gradiente de índice. En este régimen, las reflexiones internas se reducen fuertemente y, en configuración axisimétrica, la adaptación de simetría con fuentes acústicas radiando haces de sonido incrementa la eficiencia drásticamente. Además, la teoría de homogenización puede ser empleada para modelar la estructura como un medio efectivo con propiedades físicas efectivas, permitiendo el estudio del frente de ondas en términos refractivos. Se mostrará el modelado, diseño y caracterización de un dispositivo de focalización eficiente basado en los conceptos anteriores. Considérese ahora una estructura periódica en la que uno de los parámetros de la red, sea el paso de red o el factor de llenado, cambia gradualmente a lo largo de la dirección de propagación. Los cristales chirp representan este concepto y son empleados aquí para demostrar un mecanismo novedoso de incremento de la intensidad de la onda sonora basado en un fenómeno conocido como reflexión "suave". Este incremento está relacionado con una ralentización progresiva de la onda conforme se propaga a través del material, asociado con la velocidad de grupo de la relación de dispersión local en los planos del cristal. Un modelo basado en la teoría de modos acoplados es propuesto para predecir e interpretar este efecto. Se observan dos fenómenos diferentes al considerar pérdidas en estructuras periódicas. Por un lado, si se considera la propagación de ondas sonoras en un array periódico de capas absorbentes, cuyo frente de ondas es paralelo a los planos del cristal, se produce una reducción anómala en la absorción combinada con un incremento simultáneo de la reflexión y transmisión a las frecuencias de Bragg, de forma contraria a la habitual reducción de la transmisión, característica de sistemas periódicos conservativos a estas frecuencias. En el caso de la misma estructura laminada en la que se cubre uno de sus lados mediante un reflector rígido, la incidencia de ondas sonoras desde un medio homogéneo, cuyo frente de ondas es perpendicular a los planos del cristal, produce un gran incremento de la fuerza de / [CA] Els cristalls fonònics són materials artificials formats per una disposició d'inclusions en un medi, ambdós poden ser sòlids o fluids. Controlant la geometría i el contrast d'impedàncies dels seus materials constituents, és poden controlar les propietats dispersives de les ondes, permetent una gran varietatde fenòmens fonamentals interessants en el context de la propagació d'ones. Quan una ona propagant troba un medi amb pèrdues amb propietats físiques diferents es pot transmetre i reflectir, però també absorbida si la dissipació es té en compte. Aquests fenòmens fonamentals s'han explicat clàssicament en el context de medis homogenis, però també ha sigut un tema de creixent interés en el context d'estructures periòdiques en els últims anys. Aquesta tesi doctoral tracta de l'estudi de diferents efectes en cristalls fonònics i sònics lligats a la transmissió, reflexió i absorció d'ones, així com del desenvolupament d'una tècnica de caracterització de les propietats dispersives, descrites mitjançant la estructura de bandes. En primer lloc, s'estudia el control de la propagació ondulatori en transmissió en sistemes conservatius. Més específicament, el nostre interés és mostrar com els cristalls sonors poden modificar la dispersió espacial d'ones propagants donant lloc al control de l'amplària per difracció dels feixos sonors. Mitjançant les corbes dispersió espacial obtingudes de l'anàlisi de l'estructura de bandes, es prediu, en primer lloc, la difracció d'ones zero i negativa a freqüències próximes al final de banda. El resultat és la collimació i focalització de feixos sonors dins i darrere de cristalls de so. Després es mostra amb mesures experimentals. L'eficiència de focalització d'un cristall de so 3D està limitada per la gran dispersió d'ones dins del cristall, que és característic del règim difractiu. Per a superar aquesta limitació, estructures axisimètriques que treballen en el règim de llargues longituds d'ona, i es comporten com a lents de gradient d'índex. En aquest règim, la dispersió es redueix enormement i, en una configuració axisimètrica, a causa de l'acoblament de la simetría amb les fonts acústiques que radien feixos sonors, l'eficiència de radiació s'incrementa significativament. D'altra banda, la teoria d'homogeneïtzació es pot utilitzar per a modelar, dissenyar i caracteritzar un dispositiu eficient de focalització basat en aquests conceptes. Considerem ara una estructura periòdica en la qual un dels seus paràmetres de xarxa, com ara la constant de xarxa o el factor d'ompliment canvia gradualment al llarg de la direcció de propagació. Els cristalls chirped representen aquest concepte i s'utilitzen ací per a demostrar un mecanisme nou d'intensificació d'ones sonores basat en el fenòmen conegut com a reflexió "suau". La intensificació està relacionada amb la alentiment progressiva de l'ona conforme propaga al llarg del material, que està associada amb la velocitat de grup de la relació de dispersió local en els diferents plànols del cristall. Es proposa un model basat en la teoria de modes acoblats per a predir i interpretar este efecte. Dos fenòmens diferents cal destacar quan es tracta d'estructures periòdiques amb dissipació. Per un costat, al considerar la propagació d'ones sonores en el plànol en un array periòdic de capes absorbents, s'observa una disminució anòmala de l'absorció i es combina amb un augment simultani de reflexió i transmissió en les freqüències de Bragg que contrasta amb la usual disminució de transmissió, característica dels sistemes conservatius a eixes freqüències. Per a un medi similar de capes, amb un reflector rígid darrere, les ones fora del pla incidint l'estructura des de un medi homogeni, augmentaran considerablement la interacció. En altres paraules, el retràs temporal de les ones sonores dins del sistema periòdic augmentarà significativament produint un augmen / Cebrecos Ruiz, A. (2015). Transmission, reflection and absorption in Sonic and Phononic Crystals [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/56463 / TESIS / Premios Extraordinarios de tesis doctorales / Compendio