During the last decade, the maximum capacity of an optical fiber transmission line more than doubled every year to match the fast-growing communication need. The technology break through in dry fiber fabrication opens the possibility for fiber bandwidth all the way from 1300 nm to 1600 nm. The fast increasing demand of communication capacity results in the emergence of wavelength division multiplexing (WDM) technology, enabling tens of channels with different wavelengths transmitted simultaneously on an optical fiber. In consequence, it raises the requirement of spectral bandwidth of all the optical components used in the optical transport networking systems. Cr4+:YAG has potential to meet this demand because its 3T2¡÷3A2 transition has a strong spontaneous emission that just covers the low-loss window of optical fiber. The crystalline host offers a excellent mechanical characteristic. Such a fiber is, therefore, eminently suitable for super-wideband optical source since the required pump power is expected to be higher. We have successfully demonstrated a diode-laser pumped Cr:YAG crystal fiber ASE light source. The crystal fibers are grown by the laser-heated pedestal growth technique. Using a 46.6 mm-long Cr:YAG single crystal fiber of a 3-dB ASE width of 265 nm and a power spectral density ¡V22.1 dBm/nm was achieved. In the future, to further increase the quantum efficiency and output power we will reduce the core diameter, lengthen the fiber, increase the Cr4+ doping concentration, fabricate double-cladding, coat the fiber facets, and improve the cooling system.

Discovery of anti-cancer cisplatin was a great success in anti-cancer chemotherapy. Numerous analogues of cisplatin such as carboplatin and oxaliplatin, were developed to improve the clinical effectiveness. Nevertheless, the clinical uses of these platinum-based drugs are limited by the occurrence of drug-resistance, narrow range of susceptible cancer types and severe toxicity. These drawbacks have stimulated the development of other metal-based compounds with distinct mechanisms of anti-cancer action. In this study, a series of ytterbium(III) porphyrin and iron(II) polypyridyl complexes were synthesized. Their anti-cancer activities were examined. With the aid of gene expression profiling and bioinformatics analysis, the mechanisms of these anti-cancer active complexes have been examined. A series of ytterbium(III) porphyrin complexes have been prepared and structurally characterized. An ytterbium(III) octaethylporphyrin complex (1) was found to exhibit potent anti-cancer activities with cytotoxic IC50 values down to sub-micromolar range. Complex (1) was shown to exist as a dimeric hydroxyl-bridged complex [Yb2(OEP)2(μ-OH)2] (where H2OEP = octylethylporphyrin) in CH2Cl2 and in solid state, and as monomeric [Yb(OEP)(DMSO)(OH)(OH2)] in DMSO/aqueous solution. Unlike various anti-cancer lanthanide complexes which are commonly proposed to target cellular DNA, our transcriptomics data, bioinformatics connectivity map analysis and cellular experiments altogether indicate that (1) exerts its anticancer effect through apoptosis which is highly associated with endoplasmic reticulum stress pathway. Two iron(II) polypyridyl complexes [Fe(qpy)(CH3CN)2](ClO4)2 (Fe-1a) (qpy =2,2’:6’,2”:6”,2’”:6”’,2””-quinquepyridine) and [Fe(Py5-OH)(CH3CN)](ClO4)2 (Fe-2a) (Py5-OH = 2,6-bis[hydroxybis(2-pyridyl)methyl]pyridine) were found to display selective cytotoxicity towards cancer cell lines over a normal lung fibroblast cell line. Affymetrix oligonucleotide microarray and bioinformatics analysis suggested that the anti-cancer mechanisms of Fe-1a and Fe-2a involve apoptosis, cell cycle arrest, activation of p53 and mitogen activated protein kinase (MAPK). Complex Fe-1a induced the formation of reactive oxygen species (ROS) in a concentration-dependent manner. Both iron complexes could cleave supercoiled plasmid DNA. The cellular DNA damage induced by both complexes was confirmed by comet assay and phospho-histone protein ( -H2AX) immunofluorescence assay. Cell cycle progression analysis revealed that Fe-1a induced both S- and G2/M-phase cell cycle arrests, whereas Fe-2a induced a G0/G1-phase arrest. Apoptosis induced by both complexes was confirmed by annexin-V/SYTOX green flow cytometry analysis and western blotting. Moreover, p53 and MAPK activation were found to be associated with the induced apoptosis. By employing the cationic porphyrin ligand, 5-(p-N-methylpyridyl)triphenylporphyrin [H2(5-MePyTPP)]+, a series of cationic metalloporphyrin complexes formulated as [M(porphyrinato)]n+ (where M = PtII, RuII, CoII or AuIII, n = 1 or 2) were prepared. The cytotoxicities of these complexes were examined. The platinum(II) and ruthenium(II) complexes were relatively non-cytotoxic towards the examined cancer cell lines with IC50 >24 μM. [CoII(5-MePyTPP)]Cl displayed a more pronounced anti-cancer activity with IC50 values between 7.48 – 17.7 μM. However, this Co(II) complex displayed poor selectivity towards the cancer cell lines compared to the normal cell line. The gold(III) porphyrin complex [AuIII(5-MePyTPP)]Cl2 showed a much higher potency (IC50 =3.01 -10.7μM) than the other [M(5-MePyTPP)]n+ prepared. By means of flow cytometry and fluorescence microscopy, [AuIII(5-MePyTPP)]Cl2 was found to induce G2/M-phase cell cycle arrest and necrotic cell death in HeLa cells. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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Orientador: Keizo Yukimitu / Banca: José Brás Barreto Oliveira / Banca: Noelio Oliveira Dantas / Resumo: Neste trabalho foi estudado o sistema vítreo (100-x)% (80% TeO2-20% WO3)-(x)% Yb2O3, onde x = 0; 0,1; 0,2; 0,3; 0,4 e 0,5%. As técnicas de difração de raios-X, espectroscopia no infravermelho, espectroscopia Raman e espectroscopia no UV-Vis foram usadas para caracterizar os efeitos da dopagem sobre as propriedades estruturais e ópticas dos vidros estudados. Usando os dados de espectroscopia na região espectral ultravioleta-visível foi possível observar que não houve mudança das freqüências de corte para cada composição e ainda calcular a energia de "gap" e a energia de cauda de Urbach. Usando os dados de fotoluminescência observam-se picos que indicam o desdobramento dos níveis de energia dos estados 2F7/2 e 2F5/2 dos íons de Yb3+. Para os comprimentos de onda de excitação de 514,5 a 488,0 nm, crescem as taxas de absorção do sistema vítreo TW, transferência de carga para o estado 2F5/2 do Yb3+ e da transição radiativa 2F5/2 2F7/2, aumentando, desta forma, a intensidade da fotoluminescência. Já para os comprimentos de onda de excitação 457,9 e 476,5 nm as taxas de absorção do sistema vítreo TW, a transferência de carga para o estado 2F5/2 do Yb3+ e a transição radiativa 2F5/2 2F7/2 são as mesmas e, consequentemente, a intensidade da fotoluminescência é constante. / Abstract: This work presents the study on the glassy system (100-x)% (80% 20% TeO2-WO3) - (x)% Yb2O3 where x = 0, 0.1, 0.2, 0.3, 0.4 and 0 5%. The techniques of X-ray diffraction, infrared spectroscopy, Raman spectroscopy and UV-Vis were used to characterize the effects of Yb doping on the structural and optical properties of the glasses. Using data from spectroscopy ultraviolet-visible spectral region was observed that there was no change of cutting frequencies for each compound and were calculate the energy gap and Urbach tail energy. Using the data of photoluminescence peak is observed indicating the splitting of energy levels of states 2F7/2 and 2F5/2 of Yb3+ ions. The rate of electron transition probability is influenced by temperature. To the excitation wavelength of 514.5 to 488.0 nm, growing rates of absorption of the glass system TW, charge transfer to the state 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2, increasing thus the photoluminescence intensity. As for the excitation wavelength of 476.5 and 457.9 nm absorption rates of the TW glass system, the charge transfer state to the 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2 are the same and, hence the photoluminescence intensity is constant. / Mestre

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Made available in DSpace on 2014-10-09T12:54:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:23Z (GMT). No. of bitstreams: 0 / O emissor - 177Lu é um radioisótopo terapêutico promissor para o tratamento curativo de câncer usando proteínas marcadas. Possui meia-vida de 6,71 dias e energia - máxima e média de 421 e 133 keV, respectivamente, resultando na radiação de em uma pequena área do tecido. O decaimento é acompanhado pela emissão de raios-g com baixa energia de 208 keV (11%) e 113 keV (6,4%), adequados para a aquisição de imagens. O 177Lu pode ser produzido por dois métodos diferentes, diretamente, irradiando-se alvos naturais de óxido de lutécio (Lu2O3) (176Lu, 2,6%) ou em alvos de Lu2O3 enriquecidos (em 176Lu), e também indiretamente, irradiando-se os alvos de óxido de itérbio (Yb2O3), acompanhado pela separação radioquímica dos isótopos de lutécio e itérbio. O objetivo deste trabalho é o desenvolvimento de um método de produção do 177Lu através de reação nuclear (n, g), tanto pelo método direto de produção, como pelo método indireto de produção. Foram irradiados alvos de óxido de lutécio e de itérbio para a avaliação da atividade produzida e a separação química do lutécio e do itérbio foi estudada utilizando diferentes resinas de troca de íons. Para a produção direta, o melhor resultado obtido foi utilizando o alvo Lu2O3 enriquecido em 39,6%. Já pelo método indireto de produção os melhores resultados obtidos foram com o processo de separação no qual se utiliza o -HIBA 0,25M como eluente. Pelos resultados obtidos é possível produzir o 177Lu de baixa atividade específica para o uso na marcação de moléculas destinadas ao alívio de dor óssea e para radiosinoviortese. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN/CNEN-SP

This thesis focuses on research I have done on ytterbium-doped femtosecond fiber lasers. These lasers operate in the near infrared region, lasing at 1030 nm. This wavelength is particularly important in biomedical applications, which includes but is not limited to confocal microscopy and ablation for surgical incisions. Furthermore, fiber lasers are advantageous compared to solid state lasers in terms of their cost, form factor, and ease of use. Solid state lasers still dominate the market due to their comparatively high energy pulses. High energy pulse generation in fiber lasers is hindered by either optical wave breaking or by multipulsing. One of the main challenges for fiber lasers is to overcome these limitations to achieve high energy pulses. The motivation for the work done in this thesis is increasing the output pulse peak power and energy. The main idea of the work is that decreasing the nonlinearity that acts on the pulse inside the cavity will prevent optical wave breaking, and thus will generate higher energy pulses. By increasing the output energy, ytterbium-doped femtosecond fiber lasers can be competitive with solid state lasers which are used commonly in research. Although fiber lasers tend to lack the wavelength tuning ability of solid state lasers, many biomedical applications take advantage of the 1030 µm central wavelength of ytterbium-doped fiber lasers, so the major limiting factor of fiber lasers in this field is simply the output power. By increasing the output energy without resorting to external amplification, the cavity is optimized and cost can remain low and economical. During verification of the main idea, the cavity was examined for possible back-reflections and for components with narrow spectral bandwidths which may have contributed to the presence of multipulsing. Distinct cases of multipulsing, bound pulse and harmonic mode-locking, were observed and recorded as they may be of more interest in the future. The third-order dispersion contribution from the diffraction gratings inside the laser cavity was studied, as it was also considered to be an energy-limiting factor. No significant effect was found as a result of third-order dispersion; however, a region of operation was observed where two different pulse regimes were found at the same values of net cavity group velocity dispersion. Results verify the main idea and indicate that a long length of low-doped gain fiber is preferable to a shorter, more highly doped one. The low-doped fiber in an otherwise equivalent cavity allows the nonlinear phase shift to grow at a slower rate, which results in the pulse achieving a higher peak power before reaching the nonlinear phase shift threshold at which optical wave breaking occurs. For a range of net cavity group velocity dispersion values, the final result is that the low doped fiber generates pulses of approximately twice the value of energy of the highly-doped gain fiber. Two techniques of mode-locking cavities were investigated to achieve this result. The first cavity used NPE mode-locking which masked the results, and the second used a SESAM for mode-locking which gave clear results supporting the hypothesis.