This thesis deals with solving of the Rubik's cube. It describes the Rubik's cube and the famous methods for its composition. The main goal of this work is to propose an evelutionary method that for any configuration of blocks will lead to its composition. The theis describes the problem encoding, the proposed evelutionary algorithm and its proper configuration and deployment. The achieved results are commented on and compared with other known mehtods in conclusions.

Establishing highly sophisticated polymer films for delivery systems in a biological environment and bioanalytical tasks, the formation, thickness, swelling behavior, and (physiological) stability of highly biocompatible polyelectrolyte multilayers (PEMs) are described. These PEMs are composed of the very weak polycation maltose-modified hyperbranched poly(ethyleneimine) (PEI-Mal), strongly polyanion heparin sodium salt (HE − Na +) or weakly charged polyanion hyaluronic acid sodium salt (HA-Na+) deposited on Si wafer substrates. Two different glyco architectures for PEI-Mal are used, characterized by two different degrees of maltose decoration on a PEI scaffold. Using three pH-dependent deposition approaches for optimizing the (physiological) PEM stability and swelling, PEMs are characterized by (in situ) ellipsometry, atomic force microscopy (AFM), and (in situ) attenuated total reflection-Fouriertransform infrared (ATR-FTIR). Thus, PEMs reveal significantly different thicknesses, growth mechanisms (linear versus exponential), and swelling behavior in dependence of both the polycation architectures and the deposition protocol. These PEMs will allow the study of their complexation and release properties as preswollen PEMs against anionic drug molecules, adenosine triphosphate sodium salt (ATP), especially under physiological conditions for future drug delivery coatings.

<div> As hybrid 2D materials are incorporated into next-generation device designs, it becomes more and more pertinent that methods are being developed which can facilitate large-area structural control of noncovalent monolayers assembled at 2D material interfaces. Noncovalent functionalization is often leveraged to modulate the physical properties of the underlying 2D material without disrupting the extended electronic delocalization networks intrinsic to its basal plane. The bottom-up nanofabrication technique of self-assembly permits sub-10-nm chemical patterning with low operational costs and relatively simple experimental designs.</div><div> The Claridge Group is interested in leveraging the unique chemical orthogonality intrinsic to the cellular membrane as a means of creating sub-10-nm hydrophilic-hydrophobic striped patterns across 2D material interfaces for applications ranging from interfacial wetting to large-area molecular templates to guide heterogeneous nanoparticle assembly. Using Langmuir–Schaefer conversion, standing phases of polymerizable amphiphiles at the air-water interfaces of a Langmuir trough are converted (through rotation) to lying-down phases on 2D material substrates. Using room temperature substrates, transfer of amphiphiles to a lowered substrate results in small domains and incomplete surface coverage.</div><div> Recognizing that heating the substrate during the LS conversion process may lower the energy barriers to molecular reorientation, and promote better molecular domain assembly, we developed a thermally controlled heated transfer stage that can maintain the surface temperature of the substrate throughout the deposition process. We found that heating during transfer results in the assembly of domains with edge lengths routinely an order of magnitude larger than transfer using room temperature substrates that are more stable towards rigorous repeat washing cycles with both polar and nonpolar solvents.</div><div> To promote the effectiveness of the LS conversion technique beyond academic environments for the noncovalent functionalization 2D material substrates for next-generation device designs, we designed and built a thermally controlled rotary stage to address the longstanding scaling demerit of LS conversion. First, we report the development of a flexible HOPG substrate film that can wrap around the perimeter of the heated disk and can be continuously cycled through the Langmuir film. We found that thermally controlled rotary (TCR) LS conversion can achieve nearly complete surface coverage at the slowest translation speed tested (0.14 mm/s). TCR–LS facilitates the assembly of domains nearly 10,000 μm² which were subsequently used as molecular templates to guide the assembly of ultranarrow AuNWs from solution in a non-heated rotary transfer step. Together, these findings provide the foundation for the use of roll-to-roll protocols to leverage LS conversion for noncovalent functionalization of 2D materials. A true roll-to-roll thermally controlled LS conversion system may prove to be advantageous and a cost-efficient process in applications that require large areas of functional surface, or benefit from long-range ordering within the functional film.</div>

[EN] Fiber grating sensors and devices have demonstrated outstanding capabilities in both telecommunications and sensing areas, due to their well-known advantageous characteristics. Therefore, one of the most important motivations lies in the potential of customized fiber gratings to be suitably employed for improving the interrogation process of optical fiber sensors and systems. This Ph.D. dissertation is focused on the study, design, fabrication and performance evaluation of customized fiber Bragg gratings (FBGs) and long period gratings (LPGs) with the double aim to present novel sensing technologies and to enhance the response of existing sensing systems. In this context, a technique based on time-frequency domain analysis has been studied and applied to interrogate different kind of FBGs-based sensors. The distribution of the central wavelength along the sensing structures has been demonstrated, based on a combination of frequency scanning of the interrogating optical pulse and optical time-domain reflectometry (OTDR), allowing the detection of spot events with good performance in terms of measurand resolution. Moreover, different customized FBGs have been interrogated using a technology inspired on the operation principle of microwave photonics (MWP) filters, enabling the detection of spot events using radio-frequency (RF) devices with modest bandwidth. The sensing capability of these technological platforms has been fruitfully employed for implementing a large scale quasi-distributed sensor, based on an array of cascaded FBGs. The potentiality of LPGs as fiber optic sensors has also been investigated in a new fashion, exploiting the potentials of MWP filtering techniques. Besides, a novel approach for simultaneous measurements based on a half-coated LPG has been proposed and demonstrated. Finally, the feasibility of FBGs as selective wavelength filters has been exploited in sensing applications; an alternative approach to improve the response and performance of Brillouin distributed fiber sensors has been studied and validated via experiments. The performance of the reported sensing platforms have been analyzed and evaluated so as to characterize their impact on the fiber sensing field and to ultimately identify the use of the most suitable technology depending on the processing task to be carried out and on the final goal to reach. / [ES] Los sensores y dispositivos en fibra basados en redes de difracción han mostrado excepcionales capacidades en el ámbito de las telecomunicaciones y del sensado, gracias a sus excelentes propiedades. Entre las motivaciones más estimulantes destaca la posibilidad de fabricar redes de difracción ad-hoc para implementar y/o mejorar las prestaciones de los sensores fotónicos. Esta tesis doctoral se ha enfocado en el estudio, diseño, fabricación y evaluación de las prestaciones de redes de difracción de Bragg (FBGs) y de redes de difracción de periodo largo (LPGs) personalizadas con el fin de desarrollar nuevas plataformas de detección y a la vez mejorar la respuesta y las prestaciones de los sensores fotónicos ya existentes. En este contexto, una técnica basada en el análisis tiempofrecuencia se ha estudiado e implementado para la interrogación de sensores en fibra basados en varios tipos y modelos de FBGs. Se ha analizado la distribución de la longitud de onda central a lo largo de la estructura de sensado, gracias a una metodología que conlleva el escaneo en frecuencia del pulso óptico incidente y la técnica conocida como reflectometria óptica en el dominio del tiempo (OTDR). De esta manera se ha llevado a cabo la detección de eventos puntuales, alcanzando muy buenas prestaciones en términos de resolución de la magnitud a medir. Además, se han interrogado varias FBGs a través de una técnica basada en el principio de operación de los filtros de fotónica de microondas (MWP), logrando así la detección de eventos puntuales usando dispositivos de radio-frecuencia (RF) caracterizados por un moderado ancho de banda. La capacidad de sensado de estas plataformas tecnológicas ha sido aprovechada para la realización de un sensor quasi-distribuido de gran alcance, formado por una estructura en cascada de muchas FBGs. Por otro lado, se han puesto a prueba las capacidades de las LPGs como sensores ópticos según un enfoque novedoso; para ello se han aprovechados las potencialidades de los filtros de MWP. Asimismo, se ha estudiado y demostrado un nuevo método para medidas simultáneas de dos parámetros, basado en una LPG parcialmente recubierta por una película polimérica. Finalmente, se ha explotado la viabilidad de las FBGs en cuanto al filtrado selectivo en longitud de onda para aplicaciones de sensado; para ello se ha propuesto un sistema alternativo para la mejora de la respuesta y de las prestaciones de sensores ópticos distribuidos basados en el scattering de Brillouin. En conclusión, se han analizado y evaluado las prestaciones de las plataformas de sensado propuestas para caracterizar su impacto en el ámbito de los sistemas de detección por fibra y además identificar el uso de la tecnología más adecuada dependiendo de la tarea a desarrollar y del objetivo a alcanzar. / [CA] Els sensors i dispositius en fibra basats en xarxes de difracció han mostrat excepcionals capacitats en l'àmbit de les telecomunicacions i del sensat, gràcies a les seus excel¿lents propietats. Entre les motivacions més estimulants destaca la possibilitat de fabricar xarxes de difracció ad-hoc per a implementar i/o millorar les prestacions de sensors fotònics. Esta tesi doctoral s'ha enfocat en l'estudi, disseny, fabricació i avaluació de les prestacions de xarxes de difracció de Bragg (FBGs) i de xarxes de difracció de període llarg (LPGs) personalitzades per tal de desenvolupar noves plataformes de detecció i al mateix temps millorar la resposta i les prestacions dels sensors fotònics ja existents. En este context, una tècnica basada en l'anàlisi temps-freqüència s'ha estudiat i implementat per a la interrogació de sensors en fibra basats en diversos tipus i models de FBGs. S'ha analitzat la distribució de la longitud d'ona central al llarg de l'estructura de sensat, gràcies a una metodologia que comporta l'escaneig en freqüència del pols òptic incident i la tècnica coneguda com reflectometria òptica en el domini del temps (OTDR). D'esta manera s'ha dut a terme la detecció d'esdeveniments puntuals, aconseguint molt bones prestacions en termes de resolució de la magnitud a mesurar. A més, s'han interrogat diverses FBGs a través d'una tècnica basada en el principi d'operació dels filtres de fotònica de microones (MWP), aconseguint així la detecció d'esdeveniments puntuals utilitzant dispositius de ràdio-freqüència (RF) caracteritzats per un moderat ample de banda. La capacitat de sensat d'aquestes plataformes tecnològiques ha sigut aprofitada per a la realització d'un sensor quasi-distribuït a llarga escala, format per una estructura en cascada de moltes FBGs. D'altra banda, s'han posat a prova les capacitats de les LPGs com a sensors òptics segons un enfocament nou; per a això s'han aprofitat les potencialitats dels filtres de MWP. Així mateix, s'ha estudiat i demostrat un nou mètode per a mesures simultànies de dos paràmetres, basat en una LPG parcialment recoberta per una pel¿lícula polimèrica. Finalment, s'ha explotat la viabilitat de les FBGs pel que fa al filtrat selectiu en longitud d'ona per a aplicacions de sensat; per això s'ha proposat un sistema alternatiu per a la millora de la resposta i de les prestacions de sensors òptics distribuïts basats en el scattering de Brillouin. S'han analitzat i avaluat les prestacions de les plataformes de sensat propostes per a caracteritzar el seu impacte en l'àmbit dels sistemes de detecció per fibra i a més identificar l'ús de la tecnologia més adequada depenent de la tasca a desenvolupar i de l'objectiu a assolir. / Ricchiuti, AL. (2016). Design and fabrication of customized fiber gratings to improve the interrogation of optical fiber sensors [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/66343 / TESIS / Premios Extraordinarios de tesis doctorales

The research presented in this dissertation is focused on the construction of complex molecular structures on planar gold and silicon dioxide surfaces using a variety of surface modification techniques, along with thorough surface characterization at each modification step. The dissertation is structured into six separate chapters. In Chapter 1, an introduction to the importance and implications of molecular level surface modification, commonly employed surface modification methods, and available surface characterization techniques is presented. Chapter 2 shows applications of novel methodologies for the functionalization of gold surfaces using alkane dithiol self-assembled monolayers and thiol-ene click chemistry. The resulting functionalized gold substrates demonstrate higher chemical stability than alkanethiol self-assembled monolayers alone and allow spatially controlled functionalization of gold surfaces with light. In Chapter 3, work on tunable hydrophobic surfaces is presented. These surfaces are prepared using a combination of organosilane chemistry, layer-by-layer polyelectrolyte deposition, and thiol-ene chemistry. These hydrophobic surfaces demonstrate high mechanical and chemical stability, even at low pH (1.68). The pinning of water droplets could be tuned on them by the extent of their thermal treatment. Comprehensive surface characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), spectroscopic ellipsometry, atomic force microscopy, and water contact angles was carried out on the molecular assemblies prepared on gold and silicon dioxide surfaces. Chapters 4 and 5 are focused on the application, data interpretation, and enhancement in sensitivity of different surface characterization methods. In Chapter 4, XPS, ToF-SIMS, and principal components analysis are used to probe a real world corrosion-type problem. This systemic study showed the destruction of a protective coating composed of a nitrilotris(methylene)triphosphonic acid by a low-intensity fluorine plasma. In Chapter 5, enhancement in ToF-SIMS signals is shown via bismuth metal deposition. These surfaces are also probed by spectroscopic ellipsometry using the interference enhancement method. Finally, Chapter 6 concludes this dissertation by describing possible future work.