Along with the rapidly increasing demand for wireless data while more and more crowded radio frequency (RF) spectrum, optical wireless communications (OWC) become a promising candidate to complement conventional RF communications, especially for indoor short and medium range data transmissions. Orthogonal frequency division multiplexing (OFDM) is considered for OWC due to its ability to boost data rates. However, the average emitted optical power and dynamic range of driving signals of LEDs are two major constraints in OWC. OFDM waveforms exhibits high upper and lower peak-to-average power ratios (PAPRs), which make OFDM signals optical power inefficient and easy to violate the dynamic range of LEDs, resulting clipping and nonlinear distortions. In this dissertation, we analyze and design optical power and dynamic range constrained OWC systems, for which OFDM is our major subject. We first derive distributions of upper PAPR and lower PAPR of OWC-OFDM signals. Then we analyze the clipped OFDM signals in term of error vector magnitude (EVM), signal-to-distortion ratio (SDR), and achievable data rates under both optical power and dynamic range constraints. The next part of this dissertation is the OFDM system design for visible light communications (VLC) considering illumination requirement. We investigate the illumination-to-communication efficiency (ICE) in VLC-OFDM, and design the brightness control and flickering mitigation schemes for VLC-OFDM. In the end, to reduce the complexity of driving circuits of LEDs , we propose using delta-sigma modulators in VLC-OFDM systems to convert continuous magnitude OFDM symbols into two-level LED driver signals without loss of the communication theory advantages of OFDM.

Photocatalysis is an advanced oxidation process, which has shown to possess an enhanced capability to remove a wide range of contaminants. It involves the use of a semiconductor photocatalyst and a photon source. Photocatalysis has several advantages such as mild reaction conditions like ambient temperature and pressure, good control over the reaction and faster reaction kinetics. Semiconductor photocatalysts such as TiO2, ZnO, Fe2O3, CdS, ZnS, etc. absorbs light of energy greater than or equal to its band gap and the electron in the valence band gets excited to conduction band leaving behind the hole in valence band. These charge carrier pair results in the formation of various reactive oxygen species such as hydroxyl and superoxide radicals which results in the degradation of chemical contaminants and inactivation of microorganisms. TiO2 is the most widely used catalyst in photocatalytic studies because of its high photocatalytic activity, non-toxicity and wide availability. Anatase phase TiO2 has been reported to possess higher photocatalytic activity than the rutile phase. Although there are several methods to synthesize TiO2, solution combustion synthesis is a single step process to produce pure anatase phase TiO2. The catalyst produced by this method has been shown to be superior to the commercially available Degussa P-25 catalyst for the degradation of various chemical contaminants. The present investigation focuses on the use of combustion synthesized catalyst for the inactivation of microorganisms. The photocatalytic activity was compared with commercial Degussa P-25 catalyst. The various aspects of photocatalytic inactivation reactions studied in this dissertation are: i) photocatalytic inactivation of microorganisms in presence of UV light, ii) effect of various parameters on the inactivation, iii) photocatalytic inactivation in presence of visible light, iv) use of immobilized catalyst for the photocatalytic inactivation, v) understanding of mechanism and kinetics of inactivation. Combustion synthesized TiO2 (CS-TiO2), combustion synthesized 1% Ag substituted TiO2 (Ag/TiO2 (Sub)) and 1% Ag impregnated CS-TiO2 (Ag/TiO2 (Imp)) were used as photocatalysts. The catalysts were characterized by powder XRD, TEM, BET surface area, UV-Vis spectroscopy, TGA and photoluminescence spectroscopy. The photocatalytic inactivation experiments were carried out using E. coli (K-12 MG 1655), a bacterial strain and P. pastoris (X-33), a yeast strain, as model microorganisms. The results demonstrate higher photocatalytic activity of all the combustion synthesized catalysts than commercial Degussa P-25 catalyst. The optimum catalyst concentration was 0.25 g/L and the maximum inactivation was observed in the presence of Ag/TiO2 (Imp) catalyst. Rapid and complete inactivation of the microorganisms was observed at lower initial cell concentrations. A reduced photocatalytic inactivation was observed in presence of various anions (HCO3¯ , SO4 2¯ , Cl¯ and NO3¯ ) and cations (Na, K, Caand Mg). Even a small addition of H2O2 was observed to improve the photocatalytic inactivation. At higher dosage of H2O2, a 2 min exposure was sufficient to result in a complete inactivation. Changing the initial pH of the solution was observed to have no significant effect on the photocatalytic inactivation. All the combustion synthesized catalysts showed higher activity as compared to those obtained with commercial Degussa P-25 TiO2 in presence of visible light. The higher photocatalytic activity of combustion synthesized TiO2 can be attributed to the lesser crystallite size, higher surface area, large amount of hydroxyl groups and decreased band-gap energy of the catalyst. The present study demonstrates the potential use of catalyst immobilized thin films for the photocatalytic inactivation of E. coli in the presence of UV light. The CS-TiO2 catalyst was immobilized on glass substrate by LbL deposition technique. The performance of immobilized CS-TiO2 was compared to commercial Degussa Aeroxide TiO2 P-25 (Aeroxide) catalyst. The effect of various operating parameters like catalyst loading, surface area and number of bilayers on inactivation has been investigated. It was observed that increasing the number of bilayers and the concentration did not influence the inactivation but increased surface area led to an increase in inactivation. It was observed that the catalyst immobilized on glass slides can be used for repeated experimental cycles with the same efficiency. It was observed that the inactivation process can be studied in continuous mode by using catalyst immobilized on glass beads. The work also focused attention towards understanding the microorganism inactivation mechanism and kinetic aspects. Various microscopy techniques such as optical microscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the inactivation mechanism. From the images obtained, it was suggested that the inactivation is caused due to rupture of cell wall. The mechanism was also examined by carrying out degradation experiments on cell component such as protein and media component such as dextrose. UV alone was observed to degrade protein and the presence of catalyst showed no additional effect. On the other hand, dextrose does not respond to photocatalytic degradation even at a lower concentration. The photocatalytic degradation of Orange G dye was reduced by addition of dextrose sugar or protein which shows a possibility of competitive degradation. The kinetics of inactivation was studied by various models available in literature such as the power-law model, Chick-Watson model, modified Hom model, GInaFIT tool and a Langmuir-Hinshelwood type model. It was observed that power-law based kinetic model showed good agreement with the experimental data. A mechanistic Langmuir-Hinshelwood type model was also observed to model the inactivation reactions with certain assumptions.

extilindustrin måste ständigt söka nya alternativ inom beläggningar och laminering för att minska den skadliga miljöpåverkan. En fråga som uppkommit är om beläggningar används i större utsträckning än vad som egentligen behövs. Denna kandidatuppsats har skrivits i samarbete med Artex AB och kretsar kring ett befintligt solskydd och solens ljusspektrum som består av strålar mellan 320–2500 nm. Material som bestrålas kan antingen absorbera, reflektera eller transmittera dessa strålar. Strålarnas alternativa vägar adderat med varandra blir alltid hundra procent, vilket innebär att genom att öka den reflekterande förmågan minskas de andra två tillstånden. I denna studie granskas den totala reflekterande förmågan av ljusspektrumet hos textila material som i sin tur beror på många olika faktorer. Det undersöks även om det är ett steg i fel riktning att använda sig av beläggningar för att nå ett bättre högreflekterande material. Detta även för att minska miljöbelastningen. Eftersom beläggningar generellt förstyvar material är detta kontraproduktivt när man vill bibehålla följsamheten hos en tygvara, vilket är avgörande för denna typ av produkt. Skrynkelheten går nämligen hand i hand med tygvarans då stumma yta. Detta projekt fokuserar på solskydd som ska användas inifrån en bil. Syftet med studien var alltså att undersöka om en obelagd vit och tät tygvara kan uppnå tillräcklig funktion för ett solskydd innanför en bil. I experimenten användes fyra olika tygvaror med olika strukturer i bindningarna för att göra en så omfattande studie som möjligt. Dessa fyra var: en satin, en varptrikå och två stycken tvåskaft, varav den ena glesare och mer matt än den andra. Respektive tygvara beströks med ett färgpigment för att analysera om kombinationen mellan reflektion och elastisk potential var möjlig. Tester som genomförts i denna undersökning var: bestämning av färghärdighet, total reflektion, ljustransmittansmätning och ett egenkomponerat skrynkeltest. Vidare granskades dess skillnader för att undersöka om ett vitt material kunde ge en bättre totalreflektion, men även för att bevisa att en tygvaras konstruktion kan erhålla följsamheten även om en beläggning är nödvändig. Mätvärdena granskades för att sedan jämföra, först med varandra och sedan mot ett referensprov som kommer från en befintlig produkt som författarna fick att tillgå från Artex AB. En trikåvaras elastiska förmåga visade sig kunna bibehållas trots ett belagt ytskikt, och visade även på bra totalreflektion. Denna varptrikå uppvisade, tillsammans med satinen, på bra totalreflektion då de var obelagda och hade god följsamhet. I test om totalreflektion visades det att en vit tät tygvara reflekterade större procent än en belagd tygvara i det synliga ljusets spektrum. För att kunna dra slutsatser om ett vitt obelagt tyg med dessa konstruktioner (satin och varptrikå) hade varit bättre för ett solskydd hade vidare undrsökningar behövts göras. Detta för att se hur mycket av den totala reaktionen som är diffus respektive spekulär / The textile industry must always find ways to reinvent itself and look for alternative options, as the coating and lamination industries are vital for a better environment. A question that needs answering is if coating on textiles are used more than needed. This bachelor thesis is written in cooperation with Artex AB and revolves around the suns light spectrum that consists of rays of 320 to 2500 nm. Materials that irradiate can either absorb, reflect or transmit these wavelengths. The rays alternative routes added with each other is always one hundred percent, which means that through increasing the reflecting capacity the other two will decrease. The most interesting part of this study, was to examine the ability of the light spectrum for material, and take in to consideration it’s construction, structure and color. Textile materials are often coated to add qualities and, in this case, to increase reflecting quality. This study is trying to prove, that it's a step in the wrong direction when it comes to the functionality of a sunshade product and for a reduced impact on the environment. As coating generally stiffens materials it’s contuerproductive with regards to keeping the resilience for the fabric, which is decisive for this type of product. The wrinkles go hand in hand with the fabrics coated surface. Since this project focuses on an existing sunshade product that will be used inside of a car, the heat radiation and the undulations within a certain wavelength that requires reflection will be focused on. The purpose with the study was to examine if an uncoated white fabric can achieve the same function in a sunshade as the current fabric in the product. In the experiments, four fabrics with different structures were used to complete such a comprehensive study as possible. These four fabrics were: one satin, one warp knitted and two plain weave, where one of them was more faint and sparse than the other. Each fabric was coated with a color pigment to analyze the possibilities of a high reflective material that still has elastic potential. The tests that were made was: determination of color fastness, total reflection, light transmit and a wrinkle test. Further on these differences were reviewed, and then concluded that the coating, in hope of increasing the reflection, is negligible. But also, to prove that a fabrics construction can keep its resilience even with a coated surface. These values have been reviewed and then compared with each other and against a reference fabric that the writers took part of from Artex AB. A warp knitted fabric was able to maintain its elastic ability regardless of a coated surface, and also shows good total reflection. This warp knitted fabric showed, together with the satin, good total reflection when they were uncoated and had good resilience. In this test for total reflection, it was proven that a white dense fabric reflects better than a coated fabric in the visible spectra of light. To be able to conclude if a white uncoated fabric with these constructions (satin and warp knitting) would be more useful for a sunshade, further studies had to be made, to see how much of the total reaction that is diffuse and specular.

Indiana University-Purdue University Indianapolis (IUPUI) / Hydrogels prepared from photopolymerization have been widely used in many biomedical applications. Ultraviolet (200-400 nm) or visible (400-800 nm) light can interact with light-sensitive compounds called photoinitiators to form radical species that trigger photopolylmerization. Since UV light has potential to cause cell damage, visible light-mediated photopolymerization has attracted much attention. The conventional method to fabricate hydrogels under visible light exposure requires usage of co-initiator triethanolamine (TEA) at high concentration (∼200 mM), which reduces cell viability. Therefore, the first objective of this thesis was to develop a new method to form poly(ethylene glycol)-diacrylate (PEGDA) hydrogel without using TEA. Specifically, thiol-containing molecules (e.g. dithiothreitol or cysteine-containing peptides) were used to replace TEA as both co-initiator and crosslinker. Co-monomer 1-vinyl-2-pyrrolidinone (NVP) was used to accelerate gelation kinetics. The gelation rate could be tuned by changing the concentration of eosinY or NVP. Variation of thiol concentration affected degradation rate of hydrogels. Many bioactive motifs have been immobilized into hydrogels to enhance cell attachment and adhesion in previous studies. In this thesis, pendant peptide RGDS was incorporated via two methods with high incorporation efficiency. The stiffness of hydrogels decreased when incorporating RGDS. The second objective of this thesis was to fabricate hydrogels using poly(ethylene glycol)-tetra-acrylate (PEG4A) macromer instead of PEGDA via the same step-and-chain-growth mixed mode mechanism. Formation of hydrogels using PEGDA in this thesis required high concentration of macromer (∼10 wt.%). Since PEG4A had two more functional acrylate groups than PEGDA, hydrogels could be fabricated using lower concentration of PEG4A (∼4 wt.%). The effects of NVP concentration and thiol content on hydrogel properties were similar to those on PEGDA hydrogels. In addition, the functionality and chemistry of thiol could also affect hydrogel properties.

[ES] La demanda de agua y la contaminación del agua son dos problemas ligados no solo de los últimos años sino también para el futuro. Mucho se ha hecho en el pasado para eliminar los contaminantes emergentes (CEC) de los sistemas acuáticos, utilizando diferentes tipos de técnicas; entre ellos, los mediados por luz han obtenido gran atención en los últimos años, debido a su alta eficiencia y sus bajos costos. Entre todas estas técnicas, se han desarrollado Procesos Avanzados de Oxidación y Reducción (AOPs y ARPs, respectivamente) para eliminar eficientemente las CECs. En detalle, en esta tesis se ha investigado el uso de moléculas orgánicas como fotocatalizadores en combinación con luz solar y visible; La riboflavina y la eosina Y han sido seleccionadas como fotocatalizadores por sus diferentes propiedades químicas: la primera es una molécula natural, conocida por sus propiedades oxidativas, mientras que la segunda es un colorante sintético. El objetivo principal de esta tesis doctoral fue investigar la degradación de varias clases de CEC mediante el uso de fotocatalizadores orgánicos y luz visible. En detalle, se monitorearon las tendencias de degradación de cada CEC frente al tiempo en diferentes condiciones de trabajo, con el fin de encontrar el mejor sistema de fotodegradación. Además, se investigó el mecanismo de funcionamiento mediante la determinación de los principales fotoproductos y mediante el estudio de las especies reactivas generadas, involucradas en los procesos. Se realizaron pruebas de toxicidad adicionales para tener una visión general de todos los participantes del sistema. Al final, toda la información se combinó para postular un mecanismo de degradación hipotético para todos los CEC. Más concretamente, la tesis se podría dividir en dos partes principales: en los capítulos 3 y 4 se llevó a cabo la oxidación de CECs, mientras que en los capítulos 5 y 6 se evaluaron las condiciones reductoras. En detalle, en los capítulos 3 y 4, se oxidaron tres compuestos farmacéuticos en presencia de riboflavina acetilada (RFTA) y luz visible. Específicamente, se investigaron carbamazepina, atenolol y noscapina en condiciones oxidativas. Los estudios de fotodegradación de los compuestos iniciales y de sus fotoproductos fueron importantes para comprender su oxidación natural en los sistemas acuosos naturales. Todas las vías oxidativas se consideraron en un mecanismo de degradación hipotético final. Además, en los capítulos 5 y 6, se investigó la fotodegradación de algunos ejemplos de estabilizadores UV de benzotriazol (BUVS). Los BUVS son compuestos muy recalcitrantes, que no se ven afectados en condiciones oxidativas. En consecuencia, se probaron múltiples sistemas fotocatalíticos y, finalmente, varios BUVS se degradaron en condiciones reductoras en presencia de RFTA o eosina Y (EOY) como fotocatalizadores, un donante de sacrificio como DABCO y luz visible. Al igual que en los capítulos anteriores, las mediciones fotoquímicas fueron necesarias para determinar la principal ruta de degradación y las especies químicas reactivas involucradas en el proceso. Se han realizado experimentos adicionales en presencia de otros donantes de sacrificio y agua marina para recrear un entorno natural real para estudios futuros. / [CA] La demanda d'aigua i la contaminació de l'aigua són dos problemes lligats no sols dels últims anys sinó també per al futur. Molt s'ha fet en el passat per a eliminar els contaminants emergents (CECs) dels sistemes aquàtics, utilitzant diferents tipus de tècniques; entre ells, els mediats per llum han obtingut gran atenció en els últims anys, a causa de la seua alta eficiència i els seus baixos costos. Entre totes aquestes tècniques, s'han desenvolupat Processos Avançats d'Oxidació i Reducció (AOPs i ARPs, respectivament) per a eliminar eficientment les CECs. Detalladament, en aquesta tesi s'ha investigat l'ús de molècules orgàniques com fotocatalizadores en combinació amb llum solar i visible; la riboflavina i l'eosina I han sigut seleccionades com fotocatalizadores per les seues diferents propietats químiques: la primera és una molècula natural, coneguda per les seues propietats oxidatives, mentre que la segona és un colorant sintètic. Detalladament, es van monitorar les tendències de degradació de cada CEC enfront del temps en diferents condicions de treball, amb la finalitat de trobar el millor sistema de fotodegradación. A més, es va investigar el mecanisme de funcionament mitjançant la determinació dels principals fotoproductos i mitjançant l'estudi de les espècies reactives generades, involucrades en els processos. Es van realitzar proves de toxicitat addicionals per a tindre una visió general de tots els participants del sistema. Al final, tota la informació es va combinar per a postular un mecanisme de degradació hipotètic per a tots els CEC. Més concretament, la tesi es podria dividir en dues parts principals: en els capítols 3 i 4 es va dur a terme l'oxidació de CECs, mentre que en els capítols 5 i 6 es van avaluar les condicions reductores. Detalladament, en els capítols 3 i 4, es van oxidar tres compostos farmacèutics en presència de riboflavina acetilada (RFTA) i llum visible. Específicament, es van investigar carbamazepina, atenolol i noscapina en condicions oxidatives. Els estudis de fotodegradación dels compostos inicials i dels seus fotoproductos van ser importants per a comprendre la seua oxidació natural en els sistemes aquosos naturals. Totes les vies oxidatives es van considerar en un mecanisme de degradació hipotètic final. A més, en els capítols 5 i 6, es va investigar la fotodegradación d'alguns exemples d'estabilitzadors UV de benzotriazol (BUVS). Els BUVS són compostos molt recalcitrants, que no es veuen afectats en condicions oxidatives. En conseqüència, es van provar múltiples sistemes fotocatalíticos i, finalment, diversos BUVS es van degradar en condicions reductores en presència de RFTA o eosina I (EOY) com fotocatalizadores, un donant de sacrifici com DABCO i llum visible. Igual que en els capítols anteriors, els mesuraments fotoquímics van ser necessàries per a determinar la principal ruta de degradació i les espècies químiques reactives involucrades en el procés. S'han realitzat experiments addicionals en presència d'altres donants de sacrifici i aigua marina per a recrear un entorn natural real per a estudis futurs. / [EN] Water request and water pollution are two bonded problems not only of the last years but also for the future. A lot has been done in the past in order to eliminate contaminants of emerging concerned (CECs) from the aquatic systems, using different kind of techniques; among them, those mediated by light have obtained great attention in the last years, due to their high efficiency and their low costs. Among all these techniques, Advanced Oxidation and Reduction Processes (AOPs and ARPs, respectively) have been developed in order to efficiently remove CECs. In detail, in this thesis the use of organic molecules as photocatalysts has been investigated in combination with solar and visible light; riboflavin and eosin Y have been selected as photocatalysts for their different chemical properties: the first is a natural molecule, well-known for its oxidative properties, while the second one is a synthetic dye. The main aim of this doctoral thesis was to investigate the degradation of various classes of CECs through the use of organic photocatalysts and visible light. In detail, degradation trends of each CEC was monitored vs time under different working conditions, in order to find the best photodegradation system. Moreover, the operating mechanism was investigated through the determination of the main photoproducts and through the study of the generated reactive species, involved in the processes. Additional toxicity tests were performed in order to have an overall view of all the participants of the system. At the end, all the information was combined to postulate an hypothetical degradation mechanism for all the CECs. More specifically, the thesis could be divided in two main parts: in chapters 3 and 4 oxidation of CECs was carried out, while in chapters 5 and 6 reductive conditions were evaluated. In detail, in chapters 3 and 4, three pharmaceutical compounds were oxidized in the presence of acetylated riboflavin (RFTA) and visible light. Specifically, carbamazepine, atenolol and noscapine were investigated under oxidative conditions. Photodegradation studies of the initial compounds and of their photoproducts were important in order to understand their natural oxidation in the natural aqueous systems. All the oxidative pathways were considered in a final hypothetical degradation mechanism. Moreover, in chapters 5 and 6, the photodegradation of a few examples of the benzotriazole UV-stabilizers (BUVSs) was investigated. BUVSs are very recalcitrant compounds, not affected under oxidative conditions. Consequentially, multiple photocatalytic systems were tested and finally, various BUVSs were degraded under reductive conditions in the presence of RFTA or eosin Y (EOY) as photocatalysts, a sacrificial donor as DABCO and visible light. As in the previous chapters, photochemical measurements were necessary to determine the main degradation pathway and the reactive chemical species involved in the process. Additional experiments in the presence of other sacrificial donors and marine water have been performed in order to recreate a real natural environment for future studies. / Pavanello, A. (2022). Novel Mechanistic Insights on the Photoredox Degradation of CECs Using Organic Photocatalysts [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191002

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Aromatic organic contaminants are difficult to biodegrade, and thus effective green technologies are required to remove these pollutants from the ecosystem. Tetracycline antibiotic, an organic water pollutant, can be degraded by heterogeneous photocatalysis using an appropriate catalyst, with capability in converting the visible light energy into active species. The thesis focused on silver nanoparticles anchored on silver bromide (Ag/AgBr) as a plasmonic catalyst dispersed on activated carbon (ACK), were used as a photocatalyst (AABR-ACK) in tetracycline removal. The aim is to develop a catalyst that is active in low intensity visible light, whilst the addition of activated carbon will increase the light absorption and separate the charge pairs, after the photocatalyst has been excited by the visible light. The activated carbons were derived from pinecone pyrolyzed in a microwave. The pinecone mass to potassium hydroxide impregnation ratio and microwave pyrolysis time influenced the activated carbon properties. An impregnation ratio of 2.24 and microwave pyrolysis time of 16 minutes at constant microwave power of 400 W yielded the activated carbon with the best-developed porous structure and electrochemical properties. This activated carbon was used during the optimisation of the Ag/AgBr activated carbon (AABR-ACK) catalysts preparation using a thermal polyol precipitation method and response surface methodology. The most active catalyst was the AABR-ACK 11 obtained by a preparation temperature of 140 ºC, time (17.50 minutes), mass of surfactant and activated carbon (0.26 g and 0.03 g) respectively. This catalyst had an ordered nanospheres morphology, reduced electron-hole recombination rate, better electrochemical properties and exhibited enhanced activity on the tetracycline antibiotic removal in comparison to other Ag/AgBr activated carbon catalysts. A percentage degradation of 92% was obtained in 180 minutes were obtained with the AABR-ACK 11 catalyst. The photocatalyst prepared using the best activated carbon derived from pinecone developed in this study was compared to photocatalysts prepared using commercial activated carbon and biochar. The Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon degraded the tetracycline to 92%, which is significantly higher than the percentage degradations (80% and 74%) for the catalyst prepared using commercial activated carbon and biochar catalysts respectively. The higher activity of the Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon was due to the conductive attributes of the catalyst support for accelerated transfer of photo-induced electrons. The Ag/AgBr activated carbon catalysts using pinecone- derived activated carbon also exhibited better performance on tetracycline removal when compared to photocatalysts reported in literature. Two catalyst preparation methods, thermal polyol and deposition precipitation, were compared. The thermal polyol method yielded a more active catalyst for the degradation of the tetracycline in comparison to the deposition precipitation method. The degradation reaction conditions such as pH, light intensity and degradation temperature influenced the rate of the reaction. The highest rate of degradation was obtained at a pH of seven, white light and 40 ºC temperature. The intermediate products formed because of hydroxylation, deamination, demethylation and dehydration during the photocatalytic degradation of tetracycline antibiotics were identified using liquid chromatography mass spectrometer. Quenching experiments with hydroxyl, hole, and superoxide anion species showed that the most important radical responsible for the tetracycline degradation was the superoxide anion radical.

Les communications optiques dans le spectre visible (VLC pour Visible-Light Communications) ont attiré une attention particulière depuis quelques années en tant qu'une solution prometteuse pour les réseaux sans fil à très haut-débit dans les milieux intra-bâtiment. Ainsi, cette technique exploite l'infrastructure d’éclairage basée sur les diodes électroluminescentes (LED) pour la transmission de l'information. Pour cette raison, elle offre de nombreux avantages, comparée aux techniques « classiques » basées sur les transmissions radiofréquences (RF), tels que l'existence d'une grande largeur de bande non réglementée, une sécurité de transmission intrinsèque et une immunité aux interférences électromagnétiques.Les principales contraintes liées à l'établissement d'une transmission VLC à très haut-débit dans ce contexte sont la propagation en trajets multiples et les caractéristiques non-idéales des LEDs commerciales, dites « blanches ». L'objectif de cette thèse est d'étudier l'impact réel de ces contraintes sur la transmission des données et de proposer des solutions efficaces de traitement du signal pour atténuer leurs effets. Nous commençons par étudier la réponse impulsionnelle du canal VLC grâce à l'élaboration d'un outil de simulation efficace. Nous évaluons ensuite la sélectivité en fréquence du canal de propagation en considérant différents critères, tels que la réponse fréquentielle, l'étalement temporelle du canal et le rapport signal à interférences. Dans un deuxième temps, compte tenu de la possibilité de la sélectivité en fréquence du canal et aussi la limitation de la bande passante des LEDs, nous étudions la pertinence de l'emploi de différentes techniques de transmission de signaux, notamment celle de l'OFDM optique (pour Orthogonal Frequency-Division Multiplexing) afin de garantir des débits de transmission compétitifs avec la RF. Etant donné le facteur de crête ou PAPR (pour Peak-to-Average Power Ratio) élevé des signaux modulés en OFDM et la dynamique limitée des LEDs, nous proposons ensuite un nouveau schéma de transmission basé sur la modulation CAP (pour Carrier-less Amplitude and Phase) en plus de l'égalisation dans le domaine fréquentiel (FDE pour Frequency-Domain Equalization) au niveau du récepteur. Nous analysons les performances des liaisons VLC utilisant cette technique et les comparons à l'OFDM optique, en prenant particulièrement en compte la non-linéarité des LEDs. Enfin, nous démontrons l'intérêt de l'utilisation du schéma de transmission CAP-FDE à travers des résultats expérimentaux. / Visible Light Communications (VLC) have attracted particular attention in the research community since a few years as a promising solution for high-speed indoor wireless networks. By exploiting the existing solid-state light-emitting diode (LED) lighting infrastructure, VLC offer numerous advantages such as a large unlicensed bandwidth, transmission security, and immunity to electro-magnetic interference compared to their radiofrequency counterparts. Within the context of indoor VLC, the multipath propagation channel and the non-ideal characteristics of the commercial white LEDs cause the main limitations for achieving high data-rate transmission. The objective of this thesis is to investigate the true impact of these limitations on the data transmission and to propose efficient signal processing solutions to mitigate their adverse effects. We start by the study of the indoor VLC channel impulse response by developing an efficient simulation tool. We then consider evaluating the channel frequency selectivity through different metrics. Next, given the potentially frequency-selective channel and the limited modulation bandwidth of the LEDs, we investigate the suitability of employing different signal transmission techniques including optical orthogonal frequency-division multiplexing (O-OFDM) in order to achieve high data-rate transmission. Given the high peak-to-average power ratio (PAPR) of O-OFDM signals and the limited dynamic range of the LEDs, we then propose a novel transmission scheme, which consists of using carrier-less amplitude and phase (CAP) modulation together with frequency domain equalization (FDE) at the receiver. We analyze the performance of the VLC link using this technique and compare it with the O-OFDM schemes, especially by taking the non-linear characteristics of the LED into account. Lastly, we demonstrate the merits of using the CAP-FDE transmission scheme via some experimental results.

Le domaine de la science des matériaux et plus particulièrement celui des matériaux hybrides suscite un intérêt croissant en raison de leurs nombreuses applications. Dans ce travail, deux stratégies synthétiques ont été considérées pour la synthèse de matériaux hybrides.Dans une première partie, nous nous sommes intéressés à une approche de synthèse directe en faisant réagir des ligands organiques de type oligophénylène avec de l’isopropoxyde de titane. Malheureusement, ces réactions ont conduit à la précipitation de solides amorphes ne permettant pas la caractérisation de ces produits.Dans une seconde partie, une approche de synthèse séquentielle qui consiste à synthétiser un objet précondensé pouvant s’auto-Assembler dans un second temps avec des ligands organiques a été proposée. Cette approche nous a conduits à synthétiser une nouvelle brique de formule Ti10O12(cat)8(pyr)8 et de trois dérivés de formules analogues Ti10O12(cat)8(pyr’)8 (pyr’ = pyridines substituées) obtenus par échange de ligands. Ces complexes, qui présentent des propriétés d’absorption dans le visible, ont été étudiés par spectroscopie d’absorption UV-Vis et grâce à des calculs théoriques. Puis nous avons utilisé le motif [Ti10O12(cat)8] pour générer des matériaux hybrides via des substitutions de ligands par des molécules polytopiques comme la 4,4’-Bipyridine et la poly(4-Vinylpyridine). / In the field of materials science, hybrid materials are of crucial importance due to their numerous applications. In this work, two strategies were considered to synthesize such hybrid materials.In a first part, we have tackled a one step synthetic approach by reacting resorcinol-Based oligophenylene organic ligands with titanium isopropoxide. Unfortunately, these reactions led to amorphous solids and no further structural information concerning these precipitates was obtained.In a second part, we have described a sequential approach which first concerns the preparation of pre-Ordered systems that are, in a second step, self-Assembled with organic linkers. Thus, our approach deals with the preparation of a new building block formulated as Ti10O12(cat)8(pyr)8 and three derivatives formulated as Ti10O12(cat)8(pyr’)8 (pyr’ = substituted pyridine) obtained by ligands exchange. These complexes exhibit visible light absorption properties that were studied through UV-Vis absorption spectroscopy and theoretical calculations. Then, the [Ti10O12(cat)8] motif was used to generate hybrid materials via ligands substitutions with polytopic ligands such as 4,4’-Bipyridine and poly(4-Vinylpyridine).

Microplastics take hundreds to thousands of years to degrade in nature, and pose a threat to the environment. A photocatalytical degradation method have been developed to take advantage of solar light to degrade microplastics, however it takes several months to degrade microplastics with the process. The purpose of this study is to enhance the degradation rate of microplastics by synthesizing a material where photocatalysis is combined with Fenton reaction. A material with zinc oxide nanorods coated with tin oxide and decorated with iron particles (𝑍𝑛𝑂/𝑆𝑛𝑂2/𝐹𝑒0) was synthesized and used to degrade methylene blue, polystyrene and polypropylene. The result show that the degradation rate with a 𝑍𝑛𝑂/𝑆𝑛𝑂2/𝐹𝑒0 – sample is faster than with a 𝑍𝑛𝑂 – sample, and that it can be used to degrade polystyrene and polypropylene.Students’ view on researchers can affect the development of their interest and attitude towards science. Study visits to laboratories have been used to increase students’ interest and give them new experiences. The purpose of this study is to investigate what and how high school students learn during a study visit to a nanotechnology laboratory, and how the study visit affects high school students’ interest and motivation for research and learning. A study visit with 5 stations was organized, and students were given a questionnaire about what they learned during the study visit. Thematic analysis was used to analyze the students’ answers. The result shows that the study visit increased students’ interest in research, and the importance of designing stations so that they are connected to students’ previous knowledge and are within their proximal development zone. / Mikroplaster tar hundratals till tusentals år att bryta ner i naturen och utgör ett hot mot miljön. En fotokatalytisk nedbrytningsprocess har utvecklats där solljus utnyttjas för att bryta ner mikroplaster, dock tar det flera månader att bryta ner mikroplaster med den processen. Syftet med denna studie är att förbättra nedbrytningshastigheten av mikroplaster genom att syntetisera ett material där fotokatalys kombineras med Fenton-reaktion. Ett material med zinkoxid nanorör belagda med tennoxid och dekorerade med järnpartiklar (𝑍𝑛𝑂/𝑆𝑛𝑂2/𝐹𝑒0) syntetiserades och användes för att bryta ner metylenblått, polystyren och polypropen. Resultatet visar att nedbrytningshastigheten med 𝑍𝑛𝑂/𝑆𝑛𝑂2/𝐹𝑒0 – materialet är snabbare än med ett 𝑍𝑛𝑂 – material, och att 𝑍𝑛𝑂/𝑆𝑛𝑂2/𝐹𝑒0 – materialet kan användas för att bryta ned polystyren och polypropen.Elevers syn på forskning och forskare kan påverka utvecklingen av deras intresse och inställning till vetenskap. Studiebesök på laboratorier har använts för att öka elevernas intresse och ge dem nya erfarenheter. Syftet med denna studie är att undersöka vad och hur gymnasieelever lär sig under ett studiebesök i ett nanotekniklaboratorium och hur studiebesöket påverkar gymnasieelevernas intresse och motivation för forskning och lärande. Ett studiebesök med 5 stationer organiserades och eleverna fick ett frågeformulär om vad de lärde sig under studiebesöket. Tematisk analys användes för att analysera elevernas svar. Resultatet visar att studiebesöket ökade elevernas intresse för forskning och vikten av att utforma stationer så att de är kopplade till elevernas tidigare kunskaper och ligger inom deras proximala utvecklingszon.