Organic light-emitting diode (OLED) technology has found multitudinous applications in the development of solid-state lighting, flat-panel displays and flexible screens. Nowadays, the phosphorescent OLEDs based on metallophosphors can reach sufficiently high efficiencies for practical application. Recently, red, green and blue (RGB) platforms of highly efficient phosphorescent emitters have been achieved and OLEDs TV is now commercialized in the marketplace. However, the design and synthesis of innovative emitter materials play an important role in commercialization of the OLED technology. The basic concept of OLED is herein discussed in chapter 1 putting main focus on phosphorescent iridium(III) complexes. In chapter 2, a series of cyclometalated iridium(III) complexes containing 2-(4-benzylphenyl)pyridine have been synthesized and different electron-donating and electron-withdrawing substituents were attached on the pyridyl ring in the ligand. The device D6 doped with 8 wt% B4 gave the excellent OLED performance with a peak of external quantum efficiency (ext) of 21.4%, power efficiency (P) of 51 lm/W and current efficiencyL) of 76.3 cd/A, which is much higher than that of commercial available fac-Ir(ppy)3 under the same operation condition. These findings draw our attention to the fact that a weak electron-donating benzyl group could alleviate intermolecular aggregation in the solid state, thus improving the device performance. The bulky moiety introduced on 2-phenylpyridine through a CH2 spacer in the ligands could suppress the triplet-triplet annihilation in their metal complexes. Cylcometalating ligands and their respective metal complexes have been fully characterized by 1H and 13C NMR spectroscopy and matrix-assisted laser desorption inoization-time of flight (MALDI-TOF) mass spectrometry. In chapter 3, a series of thiazole-based iridium(III) complexes have been synthesized and characterized. It is considered that the thiazole moiety is infrequently used for organic semiconducting materials. To have a better understanding on this functional unit, different hole-transporting groups (eg, carbazole or fluorene) are attached to the thiazole ring in the cyclometalating ligands in order to tune the HOMO and LUMO levels of the complexes. Device D29 doped with 8 wt% T2 gave the highest L of 35.8 cd/A and ext of 11.1%. This result implied that thiazole moiety is an alternative option to afford a new class of cyclometalating ligands for OLED research. In chapter 4, a series of cationic iridium(III) complexes bearing diimine ligand have been synthesized and characterized. The diimine ligands were decorated with the sterically bulky groups. As self-aggregation could deteriorate the device efficiency, this molecular design strategy can diminish the aggregation-caused quenching problems, which has been supported by the aggregation-induced emission enhancement present in complexes E2 and E3. In Chapter 5, a series of bis-tridentate iridium(III) complexes have been synthesized and characterized. Our challenging is to design two types of tridentate chelates (ie. monoanionic and dianionic ligands) for balancing the charge on the metal center. Besides, these chelates should be a good cyclometallate to coordinate with the iridium metal. Four compounds with different dianionic tridentate chelates were designed to achieve distinct color emission. Compound K4 exhibited extremely high quantum yield of 85.5%. This finding revealed that the metal complex featuring two tridentate chelates is a promising phosphorescent dye in OLED. Lastly, the concluding remarks and the experimental details of all the compounds in the previous chapters were included in Chapters 6 and 7.

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The structural design, synthesis and characterization of luminogens with aggregation-induced emission (AIE) properties are studied in this thesis. The remarkable emission properties, thermal stability and biocompatibility of the AIE-active materials demonstrate the promising applications in bioimaging and organic light-emitting diodes (OLEDs).;Chapter 1 introduces the existence of aggregation-caused quenching (ACQ) effect in most conventional organic dyes as well as phosphorescent transitional metal complexes. Discovery of AIE and its mechanical study allow further exploration of usage in organic luminescent materials. This chapter also gives some examples and the applications these AIE-active compounds.;In Chapter 2, a series of cyanostilbenes with simple electron donor (D)-p-electron acceptor (A) structure are presented and synthesized. They exhibit remarkable AIE effect as well as deep red emission peak in 95 % water fraction in THF. These results indicate that attachment of these electron acceptors provides alternative strategy for designing highly emissive AIE-active materials.;In Chapter 3, strongly emissive cyanostilbenes with phenothiazine unit are designed and synthesized. This chapter also investigates the effect of substituents in phenothiazine and terminal cyanostilbene on the photophysical properties and AIE effect. The results suggest that they are AIE-active with different sizes in nano-aggregates. Furthermore, these dyes exhibit clear and strong fluorescence in live cell imaging with excellent biocompatibility.;In Chapter 4, a series of AIE-active phosphorescent Pt(II) complexes made up of C^N^C tridentate ligands are designed and synthesized. They exhibit different morphologies and emission properties upon aggregation in 90 % water in acetonitrile although similar tridentate ligands are applied. One of the complexes in this chapter show nano-rod formation with the highest quantum efficiency in aggregated state, suggesting that rapid self-assembly process occurs to prevent non-radiative decay and oxygen quenching.;In Chapter 5, a series of bis-cyanostyryl fluorophores are designed and synthesized. They are emissive in solid state with colour range from orange to NIR region. Furthermore, they are AIE-active and some of them may contain hybridized local and charge transfer (HLCT) excited state to achieve highly efficient emission upon solvatochromic investigation. Some bis-cyanostyryl thiophenes are fabricated in OLED devices show deep-red to NIR emission, indicative of a promising way to design solid-state NIR-emissive compounds using bis-cyanostyryl derivatives.;Finally, Chapter 6 and 7 present the concluding remarks and the experimental details of the work in Chapters 2 to 5, respectively.

Vitamin D is a fat-soluble vitamin that has proven to be extremely important for human health. Vitamin D has important functions that regulate calcium and phosphate absorption from the gastrointestinal tract. The regulation of calcium and phosphorus metabolism is extremely important for the maintenance of the structural integrity of the human skeleton, neuromuscular function and a wide variety of metabolic processes. A major source of vitamin D for most children and adults if exposure to sunlight. During sun exposure 7-dehydrocholesterol in the epidermis and dermis absorb solar ultraviolet B radiation with wavelengths of 290-315nm. This results in it being converted to previtamin D. Once formed, the thermodynamically unstable previtamin D is isomerized to vitamin D. Vitamin D is then hydroxylated in the liver and the kidneys to its active form before it can act as a homeostatic regulator of calcium and phosphorus metabolism. There are certain patients who do not respond well to vitamin D supplements because they suffer from fat malabsorption syndromes such as cystic fibrosis, Crohn’s disease and ulcerative colitis. In addition, gastric bypass patients have difficulty in absorbing dietary and supplemental vitamin D. One approach for treating vitamin D deficiency in these patients is to recommend that they be exposed to artificial UVB radiation either from a tanning bed or from a Sperti vitamin D producing lamp. Novel ultraviolet emitting light emitting diodes (LED) have emerged as a promising solution because of their size, efficiency, and ability to use narrow band UV radiation. A LED has been developed to emit narrowband UVB radiation with a peak wavelength of that 295nm. This thesis provides evidence that this novel UVB-LED is able to cause the photo-conversion of 7-deyhdrocholesterol to previtamin D3 in vitro, using 7-dehydrocholesterol containing borosilicate ampoules as positive controls, as well as produce vitamin D3 in surgically obtained type II human skin. Results from this study suggest that vitamin D producing LEDs can be developed for the treatment of vitamin D deficiency, especially in patients with fat malabsorption syndromes.

This is Part B of the Thesis. / <p> The design and performance of a flat emitting ring on-axis electron gun suitable for use in a small reflected beam accelerator was investigated. The design constraints include a low emittance (approximately 5π cm mrad), and a small beam size with a focus approximately 13 cm from the emitting surface.</p> <p> A suitable geometry was determined theoretically and was tested with a dispenser cathode. A beam with a focus at 12.7 ± 1 cm and an emittance of approximately 7π cm mrad was obtained. However, the dispenser cathode response time to heater current changes is too large for the required gun current control.</p> <p> Experiments were done to study the mechanical and thermal properties of flat emitting foil rings, since a directly heated foil has a fast response time. Two foils were tested: 1.27 x 10^-3 cm thick tungsten and 4.57 x 10^-4 cm thick tantalum. The present simple design requires impractically thin foils (≤ 0.25 microns thick) to reach emission temperatures at feasible heater currents.</p> / Thesis / Master of Engineering (MEngr)

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Solar radiation influences virtually all biological process on earth. Yeasts, the microbial driver of ethanol fermentation, evolved on the surface of vegetation and had to adapt to survive photonic assault. Past research has demonstrated that white light affects yeast metabolism along with the ability to entrain circadian rhythms, although no known genetic mechanism accounts for this. High intensity narrow wavelength light-emitting diodes were employed to illuminate synthetic cultures under fermentation. Multiple colors along the visible spectrum were used, corresponding to the peak absorbance wavelengths of Saccharomyces sp. yeast. Impacts in primary metabolite evolution were found, dependent on wavelength. Longer wavelengths produced higher amounts of acetic acid and glycerol; shorter wavelengths produced more ethanol. Because past research showed light timing had pronounced effects, illumination schemes on the scale of milliseconds to hours were tested for ethanol production. Light schemes on the scale of enzymatic reactions, yeast generation times, and circadian rhythms produced the most ethanol. Discrete blocks and duration of illumination were used to elucidate where light had the most influence over yeast metabolism and fermentation. Late lag phase and mid log phase illumination impacted ethanol fermentation more than any other period of time. Light effects were tested on apple juice to see if they extended from synthetic media to natural products. Significant impacts on ethanol production were discovered and flavor/aroma impacts were noted. Light, color, intensity, and timing have all been shown to control and affect fermentation with both positive and negative effects established. / Doctor of Philosophy / Sun light influences virtually all biological process on earth. Yeasts, the microbial drivers of ethanol fermentation, evolved on the surface of vegetation and had to adapt to survive destructive effects of the sun. Past research has demonstrated that white light affects yeast metabolism along with the ability to develop growth cycles similar to day / night patterns, although it is currently not believed this possible due to the biology of yeast. High intensity single color light-emitting diodes were employed to illuminate laboratory formulated cultures under fermentation. Multiple colors along the visible spectrum were used, corresponding to the peak absorbance wavelengths of Saccharomyces sp. yeast. Green/yellow/red wavelengths produced higher amounts of acetic acid (vinegar) and glycerol; blue and ultraviolet wavelengths produced more ethanol. Because past research showed light timing could change how yeast grow and consumed carbohydrates, light timing on the scale of milliseconds to hours were tested for ethanol production. Light timing on the scale of milliseconds, hours, and daylight cycles produces the most ethanol. Discrete blocks and duration of illumination were used to find where during fermentation light had the most impact. It was found that from immediately after the beginning of fermentation to the middle of fermentation is where yeast responded the most strongly. Light effects were tested on apple juice to see if they extended laboratory cultures to natural products. Significant changes in the amount of ethanol produced were discovered and changes in the taste and smell of fermented apple juice were noted. Light, color, intensity, and timing have all been shown to control and affect fermentation with both positive and negative effects established.

The use of photonic crystals for light extraction from light-emitting diodes (LEDs) gives the possibility to shape the farfield emission pattern. This is of particular interest for étendue-limited LED applications that require a more directional farfield than state- of-the-art Lambertian emitters. However, the application of a photonic crystal in a LED results in directional emission only if the photonic crystal and the distribution of guided modes in the LED are tuned correctly. In this thesis, red- and blue-emitting thin-film PhC-LEDs in the AlGaInP and InGaN material systems were modelled, designed, fabricated and characterized. The first experimental results show that light extraction with photonic crystals from AlGaInP thin-film LEDs several microns thick is neither directional nor more efficient than state-of-the-art LEDs with a rough surface structure. Directional light extraction for AlGaInP PhC-LEDs is for the first time demonstrated in much thinner devices where the photonic crystal light extraction of guided modes is combined with the resonant-cavity effect. In an attempt to approach the ideal PhC-LED, strong photonic crystal farfield shaping is demonstrated in InGaN thin-film LEDs of sub-micron thickness. Analysis of their spectral farfields unexpectedly shows that high order diffraction contributes significantly to the light extraction efficiency if the mode absorption is sufficiently low. It is also demonstrated that directional photonic crystal light extraction is possible in InGaN thin-film LEDs several microns thick. The directionality stems from the modulation of the spontaneous emission caused by the proximity of the active region to the bottom mirror. Two new concepts for enhanced light extraction and high directionality are presented: Photonic crystals with two dominating lattice constants are found to outperform conventional photonic crystal LEDs. An alternative approach is the dielectric PhC-LED - FDTD simulations show that the high extraction efficiency of LEDs with surface roughness is combined with the higher directionality of photonic crystal light extraction.

Orientador: Raimundo Leite Cruz / Banca: Antônio de Pádua Sousa / Banca: Edmar José Scaloppi / Banca: Alexandre Barcelos Dalri / Banca: Jarbas Honório de Miranda / Resumo: Com o desenvolvimento da tecnologia dos plásticos, tornou-se possível à construção de tubos emissores, com padrão de qualidade, a custos relativamente baixos. O emprego da irrigação localizada, pelo sistema de gotejamento, ganhou no Brasil novo impulso a partir dos anos 90, com a instalação de diversas empresas internacionais especializadas neste mercado. As empresas mais importantes do mundo se fazem presente no Brasil e algumas multinacionais estão produzindo aqui parte de sua linha de produção, como: Netafim, Plastro, Amanco, NaanDan e como empresa brasileira fabricante, existe a Petroisa. Esse trabalho teve por objetivo caracterizar e avaliar de forma técnica e hidráulica alguns tubos emissores para gotejamento, comercializados no mercado brasileiro de acordo com as normas ISO 8796:2004 e ISO 9261:2004. O experimento foi conduzido no Laboratório de Irrigação do Departamento de Engenharia Rural, da Faculdade de Ciências Agronômicas, Universidade Estadual Paulista "Julio de Mesquita Filho" - Campus de Botucatu, São Paulo. A norma ISO 9261:2004 prescreve critérios para avaliar e especificar gotejadores com vazão inferior a 24 L h-1 e tem por característica principal, a flexibilidade para adaptar economicamente qualquer laboratório de irrigação, porque não especifica as características da bancada de ensaios. 2 Os ensaios visaram à determinação dos seguintes parâmetros: Coeficiente de variação de fabricação, equação característica da relação entre pressão e vazão, espessura da parede, diâmetro interno, espaçamento entre emissores, resistência à pressão hidráulica à temperatura ambiente e à temperatura de 40oC, resistência à tensão de 160 N e 180 N, e ensaio de envelhecimento precoce. As análises mostraram um coeficiente de variação de fabricação (CVf) inferior a 0,07 para todos os tubos emissores... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: With the domain of the technology of plastics, it became possible to manufacture quality emitting pipes standard, at relatively low costs. Trickle irrigation method, using emitting pipes, gained in impulse Brazil during last decade 90, with the installation of several specialized international industries. Multinationals industries such as Netafim, Plastro, Amanco, NaanDan and a Brazilian manufacturer, Petroisa are producing here part of its line of production. This work had the objective, to characterize and evaluate emitting pipes, commercialized in Brazil according to ISO 8796 and ISO 9261:2004 standards. The 4 tests were conducted in the Laboratory of Irrigation of the Faculdade de Ciências Agronômicas - Campus of Botucatu, São Paulo, Brazil. The following parameters were evaluated: manufacturing variation, pressure and discharge equation, thickness of the wall, internal diameter, emitters spacing, resistance to the hydraulic pressure at the current temperature and at raised temperature (40oC), resistance to the 160 tension and 180 N, and precocious aging. The analyses had shown manufacturing coefficients of variation below 0,07 for all the emitting pipes, (maximum value allowed by ISO 9261:2004) standard. The exponents of pressure (x), in the pressure discharge e friction were of 0.431, 0.502, 0.450, 0.575, 0.533, 0.480, 0.470 for Petro Drip, Golden Drip, Chapin, Queen Gil, Aqua Traxx, Tiran and Amanco Drip, emitters respectively, classifying them as not compensating. For ISO 9261:2004, the value of x should not exceed 0.2 to be classified as compensating. The evaluated emitters (Ram, Naan PC, Amanco Drip PC and Twin Plus) had values lesser than 0,075. The test of resistance to the tension, as ISO 9261:2004 is a useful tool to classify an emitting in reusable and not reusable pipe. Aqua Traxx emitter was classified as not reusable. It presented probably... (Complete abstract, click electronic address below). / Doutor