The breakthrough technology in dry fiber fabrication has opened the possibility for using fiber bandwidths all the way from 1.3 to 1.6£gm. However, the fiber amplifier used in commercial product, such as erbium-doped fiber amplifier (EDFA), can not fully cover the whole fiber bandwidths from 1.3 to 1.6£gm with a single fiber amplifier. Recently, the Cr4+-doped fiber has shown a broadband emission from 1.3 to 1.6£gm. Therefore, it is interesting to develop a single fiber amplifier which can operate the wide bandwidth of the 1.3~1.6£gm emission. In this study, we have successfully fabricated and measured the Cr-doped fibers by using a commercial drawing-tower technique and a rod-in-tube method. The core diameters were 26 and 16£gm. The Cr4+ fluorescence spectrum showed a broadband emission from 1.2 to 1.6£gm. The radiation intensity was up to the order of nW. This indicates that the new Cr-doped fibers may be used as a broadband fiber amplifier. The advantages of using the drawing tower to fabricate the Cr-doped fibers are to have a better control of the core diameter, the fiber uniformity and circularity. Therefore, the Cr-doped fibers may have a potential for commercial production and application to lightwave communication systems.

Cr4+:YAG is an attractive gain medium due to its broad 3-dB emission spectrum ranging from 1253 to 1530 nm, which cover the low-loss window of the silica fiber. Such a broadband haracteristic offers a potential to develop a broadband amplified spontaneous emission (ASE) light source, optical amplifier, and tunable laser. Growing the Cr4+:YAG bulk crystal into fiber form is necessary for generating larger gain by the better optical confinement of the waveguide structure. For the application of laser, it is superior to bulk crystals for reducing lasing threshold and obtain the high slope efficiency due to the beter optical confinement and heat dissipation. A record-low threshold of 0.75 mW was achieved at room temperature. It is more than 500 times lower than any previously reported Cr4+:YAG lasers, and a slope efficiency of 6.9% was obtained. The ultralow-threshold lasing is made possible by the low propagation loss of 0.08 dB/cm and the high pump intensity of the core. Such a low-threshold operation makes the double-clad crystal fiber laser be compatible to present optical communication systems. Furthermore, we demonstrate that the proposed optimization algorithm can provide an efficient and direct approach to analyzing both fiber structure and bulk medium in terms of practical application requirements. The simulation results reveal that Cr4+:YAG DCF lasers offer advantages over bulk lasers in terms of low-threshold lasing and high efficiency, which are essential for their use in optical communication systems.

The maximum capacity of an optical fiber transmission system 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 1.3 mm to 1.6 mm. The fast increasing demand of communication capacity results in the emergence of wavelength division multiplexing (WDM) technology, which results in the need for wideband optical amplifier. Cr4+:YAG has a strong spontaneous emission that covers 1.3 mm to 1.6 mm. Besides, its absorption spectrum is between 0.9 mm to 1.2 mm, which matches with the pumping source in current erbium doped optical amplifier. Such a fiber is, therefore, eminently suitable for optical amplifier applications. We have successfully fused the double cladding Cr4+:YAG crystal fiber with single mode fiber by fusion splicer. The crystal fibers are grown by the laser-heated pedestal growth technique. The splicing parameters are optimized to achieve an insertion loss of below 1 dB. Since, the core diameter tapering will increase the propagation loss and reduce the gross gain. Adiabatically tapered fiber is discussed. Simulations are performed to predict the loss, and compare with the experimental results, then find out the way to improve the gross gain. Numerical simulation indicates that the gross gain could reach 37.2 dB at 0.5 W pump, if the core diameter of the double cladding Cr4+:YAG crystal fiber is reduced to 5 mm. In the future, in order to increase gross gain we will improve the mode matching between the cores of single mode fiber and the double cladding Cr4+:YAG crystal fiber. Gradual change of the refractive index at the splicing region as well as high Cr4+ doping concentration can also improve the gross gain.

In this study, we have successfully demonstrated the use of laser scanning confocal microscopy in studying the fluorescence spectroscopy of Cr3+ and Cr4+ ions in Cr:YAG crystal fibers, double-clad crystal fibers, and glass fibers.

In the last years, intensive research on new tunable solid state laser materials has been carried out. For the spectral range from 1300 to 1600 nm the Cr4+ ion seems to be the most promising laser-ion. In order to meet the the demand of broad-band devices, we employed the Cr4+ doped YAG crystal fibers with high optical quality thin films design and coating (high index material TiO2, low index material SiO2) to achieve the development of high efficiency crystal fiber lasers. In this thesis, crystal fiber was used as the laser gain medium, and coated with optical thin films at both end faces (input face 900-1100 nm AR and 1300-1600 nm HR; output face 1300-1600 nm HR) as the laser cavity to reduce the loss and promote laser efficiency. During the experiment, we tried to optimize the coating conditions to acquire high density, stable index and low absorption coefficient thin films. With different thin film thickness and stacking designs, the electric field distribution was designed to be away from the laser interface and high index region to increase the laser-induced damage threshold and lifetime for high power pumping. In addition, CaO and Cr2O3 were deposited on Cr4+:YAG source rods before the laser-heated-pedestal growth to increase CaO and Cr2O3 doping concentration for higher fluorescence efficiency and signal saturation power.

Owing to the increasing demand on the telecommunication bandwidth and the advent of the OH--free dry fiber developed by Lucent Technology, a new transmission bandwidth for the fiber optical communication which is centered around 1400 nm has been created in recent years. However, the corresponding light sources, optical amplifiers and other devices needed in the new transmission window are still under development. This thesis is to dissert with respect to the Cr4+:YAG crystal fiber based ASE (amplified spontaneous emission) light sources which emit light with broadband wavelengths from around 1200 nm to 1600 nm. Our previous study showed that side-pumping configuration can achieve a maximum ASE power of 0.65 mW with a pump power of 11 W at 980 nm in wavelength, whereas the end-pumping configuration successfully generated an optimum ASE power of 2.45 mW with a pump power of 11 W using a 1064-nm Yb fiber laser. This thesis reviewed the Cr4+:YAG material and studied on the single and double-pumping configuration of ASE light source, numerical simulations of the L-I curve of both configurations, and of the emission and the gain spectrum of the material, plus the introductions of the experiments needed for the simulations will be reported.

Cr4+ doped Yttrium aluminum garnet (YAG) has a strong spontaneous emission that can generate near-infrared emission from 1.2 to 1.6 £gm. This broadband emission have aroused great interest in developing tunable wavelength lasers and amplified spontaneous emitter (ASE).In this dissertation, The valence states of Cr ions in Ca or Ca/Mg co-doped Cr:YAG single-crystal fibers are studied. The fibers were grown using the laser-heated pedestal growth (LHPG) method, followed by annealing treatments up to 1500 oC. The concentrations of the Cr3+ and Cr4+ ions in octahedral and tetrahedral sites in oxygen or nitrogen environments were characterized for the first time to our knowledge. Above 700 oC, migration of Cr4+ between octahedral and tetrahedral sites takes place, the ratio is about 4%; its relative stabilization energy was estimated. For Ca,Cr:YAG annealed in an oxygen or nitrogen environment, it was 0.25 and 0.3 eV, respectively. For Mg,Ca,Cr:YAG annealed in oxygen or nitrogen, it was 0.47 and 0.49 eV, respectively. For the Ca,Cr:YAG crystal fiber (Ca/Cr=113.1%) with oxygen annealing, about 35% and 2.5% of Ca ions took part in charge compensation for Cr4+ in the octahedral and tetrahedral sites, respectively. The density of oxygen vacancies depends on the concentration of Ca ions. The estimated ratios of the unreacted oxygen vacancies to total oxygen vacancies were about 63% and 88% for oxygen and nitrogen annealing, respectively. The main limitation on the concentration of Cr4+ in the tetrahedral site of YAG is the presence of unreacted oxygen vacancies. Furthermore, chromium ions tend to diffuse outward during the LHPG of YAG crystal fiber, in which the average Cr4+ ion concentration decreases significantly after each diameter-reduction step. The Cr4+ ions are replenished using an electron gun to deposit Cr2O3 and divalent-ion oxide (CaO or MgO) on the source rod circumference before growth. It was observed that Ca2+ has better efficiency to diffuse into the source rod more efficiently than Mg2+generating fewer defects and stacking faults. By CaO deposition and post growth annealing at 1350 oC under an oxygen environment, a 110% increase in Cr4+ concentration was obtained. The achieved Cr4+ concentration and the ratio of Cr4+ to total Cr were 1.76 10^18 cm^-3 and 5.5, respectively.

Submitted by Sara Ribeiro (sara.ribeiro@ucb.br) on 2017-11-08T13:12:56Z No. of bitstreams: 1 AmandaCarolineMarquesSa??deTese2016.pdf: 1482640 bytes, checksum: 98c7088a3903d189fcf2c6a44b4fcdc7 (MD5) / Approved for entry into archive by Sara Ribeiro (sara.ribeiro@ucb.br) on 2017-11-09T11:04:49Z (GMT) No. of bitstreams: 1 AmandaCarolineMarquesSa??deTese2016.pdf: 1482640 bytes, checksum: 98c7088a3903d189fcf2c6a44b4fcdc7 (MD5) / Made available in DSpace on 2017-11-09T11:04:49Z (GMT). No. of bitstreams: 1 AmandaCarolineMarquesSa??deTese2016.pdf: 1482640 bytes, checksum: 98c7088a3903d189fcf2c6a44b4fcdc7 (MD5) Previous issue date: 2016-11-01 / Bacteria are becoming resistant to a growing number of conventional antibiotics at a worrisome rate. Therefore, there is an increasing demand for new antimicrobial therapeutics. Antimicrobial peptides (AMPs) are one of promising alternatives for conventional antibiotics and are thought to be less likely to induce resistance. AMPs have been coupled to molecular scaffolds for biomedical applications such as hydrogels for wound dressings and covering implants. Here AMPs were chemically conjugated to the CR4 hydrophilic polymers. The CPF_C1 is a short peptide isolated from Xenopus clivii, the original sequence was modified one called LCPF_C1, aiming to create some distance between the first glycine and the azide added on the N terminus (on the coupled sequence). The conjugation between the AMP and the CR4 polymer used a click chemistry reaction with two steps, dependent of a hetero crosslinker (DBCO???PEG4???NHS Ester). Dynamic light scattering (DLS) and fluorimeter assays were used to evaluate the efficiency of coupling. MALDI-ToF analysis showed 3 molecules of LCPF_C1 peptide for each CR4 polymer. Moreover, microrheology showed changes on hybrids increasing the viscosity. Finally, the compounds were evaluate against four different bacteria: Staphylococcus aureus, Klebsiela pneumoneae carbapenemases (Kpc), Escherichia coli and Pseudomonas aeruginosa. It was possible to observe MIC???s against P. aeruginosa of 11 mM by using the peptide (LCPF_C1) and 55 mM for the original sequence. When the hibrids were compared to the free polymer was not found MIC values against K. pneumoneae (CR-Kp). On the other hand, the hibrids showed three times less activity than the free polymer against P. aeruginosa. No MIC values were found aganst S. aureus. Finally, against E. coli was observed a MIC value of 1000 mM for the free CR4 and 250 mM for the hibrids. On this way, the present work showed the possibility to functionalize biopolymers by using bioactive molecules coupled to biopolimers, changing the physical-chemical characteristics and increasing they applicability against bacterial infections. / Uma taxa alarmante de bact??rias tem se tornado resistente a um grande n??mero de antimicrobianos convencionais. Desta forma, a demanda por novas terapias antimicrobianas tem aumentado proporcionalmente. Assim, o uso de pept??deos antimicrobianos (PAMs) consistem em uma promissora alternativa para antibacterianos convencionais, particularmente podendo ser acoplado a estruturas moleculares para aplica????es biom??dicas, como hidrog??is para curativos e cobertura de implantes. No presente trabalho, PAMs foram quimicamente conjugados ao pol??mero hidrof??lico inspirado nas prote??nas naturais col??geno e seda CR4. O pept??deo CPF_C1 consiste em um pept??deo contendo 17 res??duos de amino??cidos isolado de Xenopus clivii, com atividade comparada ?? bact??rias Gram-negativas e -positivas. Para este estudo, a sequ??ncia original do CPF-C1 foi modificada e intitulada LCPF_C1, objetivando aumentar a dist??ncia entre a primeira glicina e a azida adicionada na por????o N-terminal. A conjuga????o entre o PAM e o pol??mero CR4 foi realizada por meio de click chemistry reaction em dois passos, dependentes do hetero crosslinker (DBCO???PEG4???NHS Ester). Ensaios de espalhamento de luz din??mico (DLS) e fluorimetria foram utilizados para avaliar a efici??ncia de acoplamento e demonstraram a presen??a do pept??deo acoplado ao pol??mero. An??lises de MALDI-ToF demonstraram 3 mol??culas do pept??deo LCPF-C1 para cada mol??cula do pol??mero CR4. Al??m disso, dados de microrreologia demonstraram mudan??as nos h??bridos como aumento de viscosidade. Finalmente, os compostos foram avaliados contra quatro bact??rias diferentes: Staphylococcus aureus, K. pneumoneae carbapenemase (Kpc), Escherichia coli e Pseudomonas aeruginosa. Foi poss??vel observar para P. aeruginosa MICs de 11 mM utilizando o pept??deo (LCPF_C1) e 55 mM para a sequ??ncia original. Quando comparados aos h??bridos em rela????o a atividade do pol??mero livre n??o foi encontrado valor de MIC contra K. pneumoneae (CR-Kp). Por outro lado, os h??bridos demonstraram um MIC cerca de tr??s vezes menor que o pol??mero livre contra P. aeruginosa. Nenhum valor de MIC foi encontrado contra S. aureus. Finalmente, contra E. coli observou-se MIC de 1000 mM para o pol??mero CR4 e 250 mM para os h??bridos. Desta forma o presente trabalho demonstrou a possibilidade de funcionalizar biopol??meros por meio do acoplamento de mol??culas bioativas, alterando suas caracter??sticas f??sico-qu??micas e aumentando sua aplicabilidade contra infec????es bacterianas.

Rapid development of fiber-optic communications network requirements increasing in recent years, The WDM technology and invention of anhydrous optical fiber open the possibility for optical fiber transmission bands broaden form 1.3 £gm to 1.6 £gm. Chromium doped yttrium aluminum garnet crystal fiber has characteristic of 300 nm broadband. Therefore, it¡¦s strongly desirable to develop a broadband fiber amplifier, laser or other active components for extending the flexibility of system architecture design in optical fiber communication. A few-mode chromium doped yttrium aluminum garnet double-clad crystalline fibers has been demonstrated by employing a modified version of LHPG technique, means using silica-YAG crystal co-drawing and multiple core-tuning process by precisely controlled inter-diffusion between YAG core and silica tube. In this thesis, electron probe x-ray micro-analysis, energy dispersive spectroscopy and transmission electron microscopy were utilized to confirm this fiber structure and composition. This fiber has gross gain about 2.3 dB with dual pumped by few hundred mini Watt. Significantly reduce the pump power threshold. Compared with the last large core size, few-mode (small core size) chromium doped yttrium aluminum garnet double-clad crystalline fibers has lower heat effect and higher power efficiency. To enhance the optical properties towards few modes or even single mode, not only reduce the transmission loss, but improve the device efficiency. Key words: Laser heated pedestal growth, Cr4+:YAG, Double-clad Crystal Fiber, gain

Submitted by Antonio Lot (antonio.lot@uol.com.br) on 2013-06-21T18:06:54Z No. of bitstreams: 1 versao final LOT.pdf: 962135 bytes, checksum: cb292bf6076c8fe3b4e332c33c200f69 (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia (suzinei.garcia@fgv.br) on 2013-06-21T19:13:40Z (GMT) No. of bitstreams: 1 versao final LOT.pdf: 962135 bytes, checksum: cb292bf6076c8fe3b4e332c33c200f69 (MD5) / Made available in DSpace on 2013-06-21T19:15:58Z (GMT). No. of bitstreams: 1 versao final LOT.pdf: 962135 bytes, checksum: cb292bf6076c8fe3b4e332c33c200f69 (MD5) Previous issue date: 2013-05-24 / Intellectual production and technological development is being dominated by just a few countries, and appear to be highly correlated with social and economic strength. Brazil, better known for its raw materials production than technology, has been developing unique capabilities to produce fuel ethanol for decades, and has become a technological differentiator, which is helping the country gain new recognition as an innovator. The continuous focus on vertical specialization of the Sugar & Ethanol sector could bring Brazil to a privileged position in the world market. It is affording the country to move beyond being a mere supplier to becoming a real value-add player for bioethanol produced out of lignocellulosic biomass. The objective of this study is, among others, to analyze the R&D efforts that resulted in Application and Publishing of patents by official organizations, such as: The United States Patent and Trademark Office - USPTO; The European Patent Office - EPO, and the Instituto Nacional (Brazilian) de Propriedade Industrial - INPI, on 'Second Generation Ethanol'. In addition, it will validate whether these efforts are impacting the competitive power among countries and patent applicant firms. After having searched and analyzed data from the aforementioned bureaux, calculations were made both on the application and publishing of patents about lignocellulosic bioethanol using the Herfindahl Hirschman Index - HHI and the Concentration Ratio - CR4, which are traditionally applied by regulating authorities to test antitrust risk for merger and acquisitions between parties in a certain market. This method allows evaluators to measure their competitiveness level / market concentration between enterprises during mergers, ramp-up, asset-buying or asset-selling processes. Mainly, if there is a risk that patent applicants have the possibility of controlling a market in the short-term, or if there is a risk of racing to negotiate royalties of the event in inventive new technologies which improve efficiency in the production of advanced ethanol. According to data published in the U.S. only a handful of companies are responsible for a high concentration of research efforts measured by the number of patent applications related to lignocellulosic bioethanol in North American enterprises. The success of those efforts, considering the total published patents, does not show concentration either in the USA or in the European Union. In Brazil there are not yet published patents shown on Lignocellulosic Bioethanol, and only one Brazilian firm has a published patent in the USA (USPTO). These results suggest that scientific research investments in Brazil is only producing scientific articles, papers, and academic / scientific degrees rather than publishing patents in specialized bureaux which would enable firms to capitalize on their inventions of methods, processes and formulations, abroad or domestically. This may mean either low research effort of this type of ethanol origination, or an asset loss by author / firm by not having the due compensation including human, intellectual and financial resources. The results of this study contribute to the discussion on the growing demand for production and consolidated supply chain of renewable energy sources, such as advanced ethanol based upon sugarcane by-product (bagasse), under marketable costs as an incremental raw material in the near future. The conclusions of this study will indicate the need of improvement on the production of applied knowledge and in focused efforts to guarantee intellectual property that contemplates asset return with royalties / Produção intelectual e desenvolvimento tecnológico podem diferenciar países e regiões no processo de desenvolvimento socioeconômico. No caso do Brasil, observa-se o papel energético do etanol combustível para veículos motorizados leves como um resultado importante do avanço tecnológico do país, que vai além da aptidão agroclimática. A contínua busca pela especialização tecnológica verticalizada do setor sucroenergético poderia levar o Brasil a uma posição, se não autônoma, mais confortável, não só de produtor de matéria-prima, mas de processos agregadores de valor no que diz respeito aos processos de produção de etanol de segunda geração, produzido a partir de biomassa lignocelulósica. O objetivo desta dissertação é analisar os esforços de P&D que resultaram em Depósitos e Publicações de patentes em órgãos oficiais como o United States Patent and Trademark Office (USPTO), o European Patent Office (EPO), e o Instituto Nacional de Propriedade Industrial (INPI), no tema etanol de segunda geração. Ainda, verifica-se se esses esforços impactam no poder concorrencial de países e firmas depositantes de patentes. Além das coletas e observações dos dados dos órgãos acima mencionados, foram calculados para os dados de depósitos e publicações de patentes no tema bioetanol lignocelulósico os índices de Herfindahl Hirschman (HHI) e a razão de concentração (Concentration Ratio) CR4, tradicionalmente utilizados para que órgãos reguladores de defesa do consumidor autorizem fusões e aquisições entre participantes de um determinado mercado. Esse método permite a observação do grau de competitividade entre as firmas depositantes de patentes no tema e a possível tendência sobre a detenção do controle em futuro próximo e a corrida para venda de royalties dos processos desenvolvidos em diferentes áreas tecnológicas para incrementar a produção industrial de etanol avançado. Os resultados indicam uma concentração elevada dos esforços de pesquisa, medidos pelos depósitos de patentes, referentes a etanol de segunda geração, em um número muito reduzido de empresas norte-americanas, quando analisada a base de dados dos EUA. O sucesso desses esforços, mensurados pela publicação de patentes, contudo, não se mostra concentrado nem nos EUA nem na União Europeia. No caso do Brasil, ainda não são encontradas publicações de patentes no tema Lignocellulosic Bioethanol, bem como apenas uma empresa brasileira possui uma patente publicada nos Estados Unidos. Esses resultados sugerem que investimentos em pesquisa científica no Brasil podem produzir mais artigos publicados e titulação acadêmica/científica que propriamente o registro de patentes em órgãos especializados em qualificar a invenção de métodos, processos ou fórmulas, dentro e fora do país. Isso pode significar tanto baixo esforço em pesquisa no assunto quanto à perda pelo autor e/ou sua instituição da oportunidade de ter seu esforço de pesquisa recompensado por meio de royalties, como compensação pela criatividade, dedicação intelectual e de recursos econômicos. Os resultados deste estudo contribuem para o debate a respeito da crescente necessidade de produção e abastecimento de fontes renováveis de energia, como o biocombustível etanol avançado à base do derivado bagaço de cana-de-açúcar, a custos mais competitivos como matéria-prima adicional e para produção incremental de etanol em futuro próximo. As conclusões do estudo indicam a necessidade do aumento na produção de conhecimento aplicado e em esforços para garantir sua propriedade intelectual, permitindo o retorno patrimonial com royalties.