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3相3元データとは，対象，変量，条件の3つの有限集合組によって表現されるデータの総称であり，マーケティングリサーチ，心理学，経済学などの様々な分野で観測されるデータである．本論文では，多変量解析手法の一つである正準共分散分析を3相3元データに拡張し，その適用例および既存手法との比較を行った． / Three-mode three-way data exist in various research areas, such as psychology and marketing research. We propose new dimensional reduction methods for three-mode three-way data based on canonical covariance analysis in this study. In addition, we include a simulation study and apply the proposed method to real data. / 博士(文化情報学) / Doctor of Culture and Information Science / 同志社大学 / Doshisha University

Ciclones são equipamentos largamente empregados na separação de partículas do ar ou na limpeza de gases de processos por ação da força centrífuga. Neste trabalho, um ciclone lavador modificado foi projetado, construído, e sua eficiência de coleta de partículas foi avaliada. O equipamento consiste de um ciclone separador tipo Americano com triplo cone, em cujo corpo cilíndrico foram introduzidos bicos nebulizadores de água. Graças a essa configuração ele pode ser usado em galpões industriais, apresenta facilidade de construção e operação e baixo custo. O autor projetou esse ciclone objetivando não somente a eficiência de coleta, mas também a compacidade, o baixo consumo de água e de eletricidade, a possibilidade de purificação de gases ou vapores tóxicos, e ainda, o resfriamento de gases quentes pela umidificação até a saturação, de acordo com os fundamentos da separação de poeiras empregada nos scrubbers úmidos. O estudo consistiu de uma avaliação experimental das condições de operação à temperaturas ambiente e superiores à ambiente, variando também a altura da chaminé e a vazão de água de umidificação da poeira. Os ensaios foram realizados em duas etapas. Na primeira, objetivou-se identificar as melhores condições de operação usando todo o potencial de variação do equipamento, e empregando um projeto fatorial de três fatores (three-way). A segunda etapa objetivou-se estimar a eficiência de coleta do ciclone lavador usando como poluente, partículas de quartzo micronizado com diâmetro médio de 7,48 µm. A concentração de partículas no gás foi de 20 a 100 mg/m3 de ar. Foi obtida uma eficiência média de 97.07±1.03 %, para 4 bicos nebulizadores, 4 aquecedores em funcionamento e altura da chaminé 645 mm, para uma vazão de gás 0,358 m3/s de gás. Concluindo a modificação do projeto aumento a eficiência de coleta de aproximadamente 70 % ,em ciclones secos, para 97,07 %. / Cyclones are devices widely employed to separate and collect particles from the air or for cleaning up gases for processes by the action of centrifugal force. In this work a modified cyclone washer was designed, fabricated, and its collection efficiency evaluated. This equipment consists of an Americantype cyclone separator with a triple cone into whose cylindrical body a spray nozzle was introduced. Thanks to its configuration, it can be used in industrial warehouses and is fairly simple to build and operate, as well as inexpensive. The author designed this cyclone with a view not only to efficiency but also compactness, low water and electricity consumption, the possibility of toxic gas or vapor absorption, the cooling of hot gases and aerosol humidification up to saturation, according to fundamentals of dust separation with wet scrubbers. The study consisted of an experimental evaluation of the operating conditions at ambient and higher than ambient temperatures, changing the chimney height and water flow rate, with the purpose of humidifying dust. The tests were carried out in two steps. The first step aimed to identify the best operating condition using the entire potential variation and employing a three-way factorial design. The second step aimed to estimate the efficiency of the cyclone washer was evaluated in the collection of micronized quartz particles with an average diameter of 7.48 µm. The amount of particles varied from 20 to 100 mg/m3 of air. An average efficiency of 97.07±1.03 % was obtained with four spray nozzles, with its four heaters turned on, chimney height of 0.645 m and 0.358 m3/s of gas. In conclusion, the design modification had increased the collection efficiency from about 70 %, in dry cyclones, to 97.07 %.

Ciclones são equipamentos largamente empregados na separação de partículas do ar ou na limpeza de gases de processos por ação da força centrífuga. Neste trabalho, um ciclone lavador modificado foi projetado, construído, e sua eficiência de coleta de partículas foi avaliada. O equipamento consiste de um ciclone separador tipo Americano com triplo cone, em cujo corpo cilíndrico foram introduzidos bicos nebulizadores de água. Graças a essa configuração ele pode ser usado em galpões industriais, apresenta facilidade de construção e operação e baixo custo. O autor projetou esse ciclone objetivando não somente a eficiência de coleta, mas também a compacidade, o baixo consumo de água e de eletricidade, a possibilidade de purificação de gases ou vapores tóxicos, e ainda, o resfriamento de gases quentes pela umidificação até a saturação, de acordo com os fundamentos da separação de poeiras empregada nos scrubbers úmidos. O estudo consistiu de uma avaliação experimental das condições de operação à temperaturas ambiente e superiores à ambiente, variando também a altura da chaminé e a vazão de água de umidificação da poeira. Os ensaios foram realizados em duas etapas. Na primeira, objetivou-se identificar as melhores condições de operação usando todo o potencial de variação do equipamento, e empregando um projeto fatorial de três fatores (three-way). A segunda etapa objetivou-se estimar a eficiência de coleta do ciclone lavador usando como poluente, partículas de quartzo micronizado com diâmetro médio de 7,48 µm. A concentração de partículas no gás foi de 20 a 100 mg/m3 de ar. Foi obtida uma eficiência média de 97.07±1.03 %, para 4 bicos nebulizadores, 4 aquecedores em funcionamento e altura da chaminé 645 mm, para uma vazão de gás 0,358 m3/s de gás. Concluindo a modificação do projeto aumento a eficiência de coleta de aproximadamente 70 % ,em ciclones secos, para 97,07 %. / Cyclones are devices widely employed to separate and collect particles from the air or for cleaning up gases for processes by the action of centrifugal force. In this work a modified cyclone washer was designed, fabricated, and its collection efficiency evaluated. This equipment consists of an Americantype cyclone separator with a triple cone into whose cylindrical body a spray nozzle was introduced. Thanks to its configuration, it can be used in industrial warehouses and is fairly simple to build and operate, as well as inexpensive. The author designed this cyclone with a view not only to efficiency but also compactness, low water and electricity consumption, the possibility of toxic gas or vapor absorption, the cooling of hot gases and aerosol humidification up to saturation, according to fundamentals of dust separation with wet scrubbers. The study consisted of an experimental evaluation of the operating conditions at ambient and higher than ambient temperatures, changing the chimney height and water flow rate, with the purpose of humidifying dust. The tests were carried out in two steps. The first step aimed to identify the best operating condition using the entire potential variation and employing a three-way factorial design. The second step aimed to estimate the efficiency of the cyclone washer was evaluated in the collection of micronized quartz particles with an average diameter of 7.48 µm. The amount of particles varied from 20 to 100 mg/m3 of air. An average efficiency of 97.07±1.03 % was obtained with four spray nozzles, with its four heaters turned on, chimney height of 0.645 m and 0.358 m3/s of gas. In conclusion, the design modification had increased the collection efficiency from about 70 %, in dry cyclones, to 97.07 %.

Secure communication is critical to many applications. To this end, various security goals can be achieved using elliptic/hyperelliptic curve and pairing based cryptography. Polynomial multiplication is used in the underlying operations of these protocols. Therefore, as part of this thesis different recursive algorithms are studied; these algorithms include Karatsuba, Toom, and Bernstein. In this thesis, we investigate algorithms and implementation techniques to improve the performance of the cryptographic protocols. Common factors present in explicit formulae in elliptic curves operations are utilized such that two multiplications are replaced by a single multiplication in a higher field. Moreover, we utilize the idea based on common factor used in elliptic curves and generate new explicit formulae for hyperelliptic curves and pairing. In the case of hyperelliptic curves, the common factor method is applied to the fastest known even characteristic hyperelliptic curve operations, i.e. divisor addition and divisor doubling. Similarly, in pairing we observe the presence of common factors inside the Miller loop of Eta pairing and the theoretical results show significant improvement when applying the idea based on common factor method. This has a great advantage for applications that require higher speed.

Detta projekt behandlar metodutveckling för att modellera en trevägskatalysator som skulle kunna användas vidare för att uppskatta utsläppen från en Ottomotor. Modellen är byggd i AVL Cruise M för att bestämma omvandlingarna för de tre lagstiftade föroreningarna kolmonoxid, kväveoxider (NOx) och metan baserat på reaktioner som sker i trevägskatalysatorer. Projektet tar också upp olika experimentella metoder och specifika kalibreringsmetoder som används för att samla in data och bygga modellen. Projektet diskuterar två olika kalibreringsprocesser baserade på insamlade experimentella data och antalet reaktioner kalibrerade i varje steg. Dessutom diskuteras programvaran som används och ändringarna som gjorts i den fördefinierade modellen av programvaran. Resultatet efter kalibreringen visade att den andra kalibreringsprocessen gav bättre resultat, men vissa avvikelser observerades i den byggda modellen. Avvikelserna antas bero på följande tre anledningar. För det första, försummar ytreaktionsmodellen föroreningarnas diffusionshastigheter. Dessutom kan komplexiteten hos objektfunktionen som matas in i optimeraren samt de stationära data som används för kalibreringsändamål också ge avvikelser. Dessa tre argument testas i projektet och slutsatserna som dras för att kunna förbättra modellen är följande.  Objektfunktionen behöver förenklas så mycket som möjligt, diffusion av föroreningar genom washcoaten kan inkluderas i olika komplicerade steg och syrelagringsreaktioner blir viktiga när man tar hänsyn till transienta förhållanden. / This project discusses about development of a method to model the three-way catalyst which could be used further to estimate the emissions from an Otto engine. The model is built in the commercial software called AVL Cruise M to determine the conversions of three legislative pollutants namely, carbon monoxide, nitrogen oxide and methane based on reactions occurring within the three-way catalyst. The project also discusses about different experimental and calibration methods used for collecting the data and building the model. The project discusses two different calibration process based on the experimental data used and number of reactions calibrated on each step. Furthermore, the software used, and the modifications made in the predefined model of the software are also discussed. The result after the calibration showed that the second calibration process gave better results, but some deviations were observed in the model built. The deviations are assumed to be because of three arguments present. Firstly, considering the surface reaction model which neglects the diffusion rates of the species. Secondly, the complexity of the objective function fed into the optimiser. The optimiser is also a software by AVL named design explorer which helps to optimise the parameters. And thirdly, the use of steady state data only and not including transient conditions for the calibration purposes. These arguments are tested in the project, and it is concluded to improve the model, the objective function needs to be simplified as much as possible, diffusion of species through washcoat could be considered at advance stages and oxygen storage reactions become important when transient conditions are taken into consideration.

Geralmente, nos experimentos genótipo por ambiente (G × E) é comum observar o comportamento dos genótipos em relação a distintos atributos nos ambientes considerados. A análise deste tipo de experimentos tem sido abordada amplamente para o caso de um único atributo. Nesta tese são apresentadas algumas alternativas de análise considerando genótipos, ambientes e atributos simultaneamente. A primeira, é baseada no método de mistura de máxima verossimilhança de agrupamento - Mixclus e a análise de componentes principais de 3 modos - 3MPCA, que permitem a análise de tabelas de tripla entrada, estes dois métodos têm sido muito usados na área da psicologia e da química, mas pouco na agricultura. A segunda, é uma metodologia que combina, o modelo de efeitos aditivos com interação multiplicativa - AMMI, modelo eficiente para a análise de experimentos (G × E) com um atributo e a análise de procrustes generalizada, que permite comparar configurações de pontos e proporcionar uma medida numérica de quanto elas diferem. Finalmente, é apresentada uma alternativa para realizar imputação de dados nos experimentos (G × E), pois, uma situação muito frequente nestes experimentos, é a presença de dados faltantes. Conclui-se que as metodologias propostas constituem ferramentas úteis para a análise de experimentos (G × E) multiatributo. / Usually, in the experiments genotype by environment (G×E) it is common to observe the behaviour of genotypes in relation to different attributes in the environments considered. The analysis of such experiments have been widely discussed for the case of a single attribute. This thesis presents some alternatives of analysis, considering genotypes, environments and attributes simultaneously. The first, is based on the mixture maximum likelihood method - Mixclus and the three-mode principal component analysis, these two methods have been very used in the psychology and chemistry, but little in agriculture. The second, is a methodology that combines the additive main effects and multiplicative interaction models - AMMI, efficient model for the analysis of experiments (G×E) with one attribute, and the generalised procrustes analysis, which allows compare configurations of points and provide a numerical measure of how much they differ. Finally, an alternative to perform data imputation in the experiments (G×E) is presented, because, a very frequent situation in these experiments, is the presence of missing values. It is concluded that the proposed methodologies are useful tools for the analysis of experiments (G×E) multi-attribute.

Among the various heterogeneous catalytic reactions three way catalysis (TWC), catalytic combustion of hydrogen, water gas shift reaction (WGS) and preferential oxidation of CO (PROX) in the hydrogen rich stream are some of the important reactions receiving the attention presently. Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) from the automobile exhaust. Catalytic combustion of hydrogen by oxygen or hydrogen-oxygen recombination reaction is an industrially important reaction. It has variety of application such as in sealed lead acid batteries and nuclear reactors. Water gas shift (WGS) reaction is of specific importance to produce hydrogen from carbonaceous material. PROX is an important step to further purify hydrogen produced form WGS. Hydrogen purified using PROX can be directly fed to polymer electrolyte membrane fuel cells. By and large, noble metals Pt, Pd, Rh, Ru and some of their alloys are dispersed on oxide or high surface area carbon are the active catalysts. An alternative approach can be to make Pt2+, Pd2+, Rh3+, Ru4+ ions substituted in reducible support such as CeO2, Ce1-xTixO2-δ and TiO2 to increase the dispersion and bring down the cost. In this thesis we have followed this new approach and show that noble metal ionic catalysts are superior to noble metal nano particles. In the 1st chapter we present an overview of heterogeneous catalysis and important heterogeneous catalytic reactions. Monolithic catalyst and various ways to coat catalysts for application have been reviewed. Metal-support interaction till date is also reviewed. In the 2nd chapter, synthesis of noble metal ionic catalysts by solution combustion method is described. Coating of washcoat and active catalyst phase over ceramic honeycomb by a new combustion method is described. Solution combustion reaction and characterization of the catalyst by x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction and reaction is given. We have fabricated experimental systems to carryout catalytic reaction and in this chapter they have been presented. In the 3rd chapter, we report a new process of coating of active exhaust catalyst over -Al2O3 coated cordierite honeycomb. The process consists of (a) growing  -Al2O3 on cordierite by solution combustion of Al(NO3)3 and oxylyldihydrazide (ODH) at 600 0C. Active catalyst phase, Ce0.98Pd0.02O2- is coated on - Al2O3 coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2  10-3 M PdCl2 solution at 500 0C. In this way a coat layer over cordierite ceramic has been achieved and catalyst has the active sites in the form of Pd2+ ions rather than Pd metal. Weight of the active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion [1]. Adhesion of catalyst to cordierite surface is via oxide growth on oxide ceramic which is very strong. 100 % conversion of CO is achieved below 80 oC at a space velocity of 880 h-1. At much higher space velocity of 21000h-1, 100 % conversion is obtained below 245 oC. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h-1 100% NO conversion is attained below 185 oC and 100 % conversion of ‘HC’(C2H2) below 220 oC. At the same space velocity 3-way catalytic performance over Ce0.98Pd0.02O2- coated monolith shows 100% conversion of all the pollutants below 220 o C with 15% excess oxygen. Catalytic activity of cordierite honeycomb coated by this new coating method for the oxidation of major hydrocarbons in exhaust gas is discussed further in this chapter. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. 3-way catalytic test is done by putting hydrocarbon mixture along with CO (10000ppm), NO (2000ppm) and O2 (15000ppm). Below 350 oC full conversion is achieved [2]. A comparison of the results shows that Ce1-xPdxO2-δ far superior to other catalysts. In this method, handling of nano material powder is avoided. In the 4th chapter we present a detailed study on the catalytic combustion of hydrogen by oxygen (hydrogen oxygen recombination reaction). Ever since Michel Faraday showed H2 + O2 recombination reaction over platinum metal plates, Pt metal has remained the only room temperature recombination catalyst. In search of an alternative catalyst, we discovered a new Pt free Ti0.99Pd0.01O2- compound which shows high rates of this reaction above 45 oC compared to Ce0.98Pt0.02O2-, Pt/Al2O3 and Pd/Al2O3. High rates of H2+O2 recombination over Pt and Pd ion respectively in CeO2 and TiO2 is due to the protonic type H2+ adsorption on Pt2+ or Pd2+ and dissociative chemisorption of O2 on the electron rich oxide ion vacancies [3]. In the case of Ce0.98Pt0.02O2-, H2/Pt ratio in a TPR experiment is ~2.3 at 0 oC. In the case of Ti0.99Pd0.01O2- also, H2 adsorption occurs below 0 oC and H2 / Pd ratio is ~2.2. Thus, more than 4-5 H atoms are adsorbed per metal ion. This is attributed to hydrogen spillover. H2 is known to be adsorbed as hydride ion (H-) over Pt, Pd, Rh, Ru, Os and Ir metals. Proton NMR studies of H2 adsorbed on Pd metal have shown upfield i.e. negative shift of 12 ppm with respect to TMS. We have studied proton NMR of Ti0.99Pd0.01O2- + H2 which show a downfield shift of 11.35 ppm confirming H+ or H2+ kind of species over Pd2+ ion in Ti0.99Pd0.01O2-. In Ce0.98Pt0.02O2- also H2 adsorption led to H2+ like species observed at 8 ppm and DFT calculations indeed showed H2+ kind species. H2+ is a precursor for dissociation and can readily induce O2 dissociation leading to high rates of recombination. In the 5th chapter we report water gas shift reaction (WGS) and preferential oxidation of CO (PROX) over Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ. The water gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nano crystalline catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2 and Ce1-xTixO2-δ. The catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS) and it has been shown that Pt2+ ions in these reducible oxides of the form Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ are highly active. These catalysts were tested for the water gas shift reaction both in presence and absence of hydrogen. It is shown that Ti0.99Pt0.01O2- exhibits higher catalytic activity than Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ [4]. Further, experiments were conducted to determine the deactivation of these catalysts by performing the daily startup and shutdown of the reactor for over 24 hours. There was no sintering of Pt and no carbonate formation and, therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ce4+, Ti4+ ions in the catalysts. Further, PROX activity of these catalysts has been studied. Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ showed high activity, large operating temperature window and low working temperature proving them to be highly effective PROX catalysts. In the 6th chapter we study the electrocatalysis of formic acid electro-oxidation and simultaneously mapping the electronic states of the electrodes by X-ray photoelectron spectroscopy (XPS). Ionically dispersed platinum in Ce1-xPtxO2-δ and Ce1-x-yTiyPtxO2-δ is very active towards oxygen evolution and formic acid oxidation. Higher electro-catalytic activity of Pt2+ ions in CeO2 and Ce1-xTixO2 compared to Pt0 in Pt/C is due to Pt2+ ion interaction with the supports, CeO2 and Ce1-xTixO2 respectively [5]. Further, ionic platinum does not suffer from CO poisoning effect unlike Pt0 in Pt/C. Utilization of lattice oxygen from the electrodes during the reaction has been demonstrated. This lattice oxygen exchange is responsible to convert CO to CO2 in the lower potential region to remove CO poisoning effect. In 7th chapter we repeat our study on the noble metal ion reducible oxide interaction in Ce1-xPtxO2- and Ce1-xPdxO2- (x= 0.02) system by a novel electrochemical method combined with XPS. Working electrodes made of CeO2 and Ce0.98Pt0.02O2- mixed with 30% carbon are cycled between 0.0-1.2 V in potentio-static (chronoamperometry) and potentio-dynamic (cyclic voltametry) mode with reference to saturated calomel electrode (SCE). Reversible oxidation of Pt0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y= 0.35) after applying +1.2 V which is not reversible. But Ce0.98Pt0.02O2- reaches a steady state with Pt2+: Pt4+ in the ratio of 0.60: 0.40 and Ce4+: Ce3+ in the ratio of 0.55: 0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V which is reversible [6]. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2- forms a stable electrode for oxidation of H2O to O2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction of Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple. Similar studies have been performed with Ce0.98Pd0.02O2- catalyst to show the redox coupling between Pd2+/Pd0 and Ce4+/Ce3+ redox couples. We expect similar redox coupling for Pd, Pt ions substituted TiO2, and Ce1-xTixO2. In the final chapter 8, a critical review and conclusion on the results presented in the thesis is presented. The combustion synthesized catalysts reported in this thesis stabilizes the Pt and Pd metals in their ionic state rather than zero valent metallic state. Thus, the catalysts are uniform solid catalysts. High activity and stability of these catalysts are shown to be due to the electronic interaction between noble metal ions and the reducible oxide. Redox couples Pt0/Pt2+, Pt2+/Pt4+ and Pd0/Pd2+ interact with Ce4+/Ce3+, Ti4+/Ti3+ couples such that metal is oxidized and the support is reduced. This has been established in the thesis by a combined use of electrochemistry and XPS thus solving a long standing problem of metal support interaction in catalysis. We hope that the results presented in the thesis is a worthwhile contribution to catalysis. (For mathematical equations pl refer pdf file.)

The cyclopentadienone-fused dihydropyrenes 46 and 47 were synthesized. The internal methyl resonances, the coupling constants, NICS calculations and X-ray results confirmed that the cyclopentadienone displays antiaromatic character resulting in bond localization in the annulene ring consistent with a 4n-pi fused system. The ring current of the dihydropyrene fragment is reduced by fusion of the antiaromatic system by about 80% of that caused by benzene. The syntheses of the methylfulvene fused dihydropyrene 56 and the phenylfulvene fused dihydropyrene 58 have been accomplished. The calculated and experimental NMR data and NICS calculations all demonstrated that the fulvenes had weak diatropic ring currents and caused bond localizations in the DHP rings, in which phenyl fulvene has a larger effect than that of methyl fulvene. A number of bis-dihydropyrene systems, bis-dihydropyrene ketone 117, bis-benzo[e]dihydropyrene ketone 119, benzo[e]dihydropyrene dihydropyrene ketone 122, bis-benzo[e]dihydropyrene methylene 124 and the benzo[e]dihydropyrene- dihydropyrene acetylene 130, have been synthesized, in which 117, 119 and 124 are homo-systems and 122 and 130 are hetero-systems. The multiple photoswitching properties study found that all of these systems except 130 showed multi-states during the photo opening and photo closing processes, which means that each end of the DHP units photo opens or closes separately rather than synchronously. In the homo switches 117, 119 and 124, the two DHP units act independently, but the relative differentiation is not very significant. On the other hand, the hetero-switch 122 showed fully differentiated photo opening process and almost a pure open-closed intermediate 122’ could be achieved. This is the first example which clearly showed four states in the UV closing process. The relative photo opening and closing rates compared to benzoDHP 36 have also been studied. It was found that while the carbonyl linker largely increased the relative photo opening rate (117, 119 and 122), the methylene linker only increased it slightly (124). The photo closing processes were always fast as usual. The studies of the thermal return reactions of these systems showed that while the carbonyl linker substantially slowed down the thermal return reactions of the DHP units (117, 119 and 122), the methylene linker speeded it up slightly (124). The mono-iron tricarbonyl benzo[e]dihydropyrene complex 152, the bis-iron tricarbonyl benzo[e]dihydropyrene complex 153 and the iron tetracarbonyl dihydropyrene complex 151 were synthesized. The structures of 152 and 153 were determined by X-ray crystallography. The coordinations of iron tricarbonyl moieties to the DHP rings caused a distortion of ca. 30 degree away from the central DHP plane. Coordination also increased bond alternation and reduced ring currents in the DHP rings. 1H-NMR and X-ray studies showed that 152 showed a weak paratropic ring current in the DHP ring. Iron coordination of the DHP completely stopped the photochromic properties of the dihydropyrenes.

Geralmente, nos experimentos genótipo por ambiente (G × E) é comum observar o comportamento dos genótipos em relação a distintos atributos nos ambientes considerados. A análise deste tipo de experimentos tem sido abordada amplamente para o caso de um único atributo. Nesta tese são apresentadas algumas alternativas de análise considerando genótipos, ambientes e atributos simultaneamente. A primeira, é baseada no método de mistura de máxima verossimilhança de agrupamento - Mixclus e a análise de componentes principais de 3 modos - 3MPCA, que permitem a análise de tabelas de tripla entrada, estes dois métodos têm sido muito usados na área da psicologia e da química, mas pouco na agricultura. A segunda, é uma metodologia que combina, o modelo de efeitos aditivos com interação multiplicativa - AMMI, modelo eficiente para a análise de experimentos (G × E) com um atributo e a análise de procrustes generalizada, que permite comparar configurações de pontos e proporcionar uma medida numérica de quanto elas diferem. Finalmente, é apresentada uma alternativa para realizar imputação de dados nos experimentos (G × E), pois, uma situação muito frequente nestes experimentos, é a presença de dados faltantes. Conclui-se que as metodologias propostas constituem ferramentas úteis para a análise de experimentos (G × E) multiatributo. / Usually, in the experiments genotype by environment (G×E) it is common to observe the behaviour of genotypes in relation to different attributes in the environments considered. The analysis of such experiments have been widely discussed for the case of a single attribute. This thesis presents some alternatives of analysis, considering genotypes, environments and attributes simultaneously. The first, is based on the mixture maximum likelihood method - Mixclus and the three-mode principal component analysis, these two methods have been very used in the psychology and chemistry, but little in agriculture. The second, is a methodology that combines the additive main effects and multiplicative interaction models - AMMI, efficient model for the analysis of experiments (G×E) with one attribute, and the generalised procrustes analysis, which allows compare configurations of points and provide a numerical measure of how much they differ. Finally, an alternative to perform data imputation in the experiments (G×E) is presented, because, a very frequent situation in these experiments, is the presence of missing values. It is concluded that the proposed methodologies are useful tools for the analysis of experiments (G×E) multi-attribute.