Considerable efforts are being devoted to designing enhanced molecular magnetic materials, in particular single molecule magnets (SMMs) that can meet the requirements for future technologies such as quantum computing and spintronics. A current trend in the field is enhancing the global anisotropy in metal complexes using single-ion anisotropy. The work in this dissertation is devoted to the synthesis and characterization of new building blocks of the highly anisotropic early transition metal ion V(III) with the aim of incorporating them into heterometallic molecular materials. The results underscore the importance of tuning the local coordination environments of metal ions in order to ensure enhanced single ion anisotropy. A family of mononuclear axially distorted vanadium (III) compounds, A[L_(3)VX_(3)] (3-9) (X = F, Cl or Br, A^(+) = Et_(4)N^(+), nBu_(4)N^(+) or PPN^(+) , L_(3) = Tp or Tp* (Tp = tris(-1-pyrazolyl)borohydride), Tp* = tris(3,5-dimethyl-1-pyrazolyl)borohydride)), and [Tp*V(DMF)_(3)](PF_(6))_(2) were studied. Replacement of the Tp ligand in 3 with the stronger π-donor Tp* results in a near doubling of the magnitude of the axial zero-field splitting parameter D_(z) (D_(z) = -16.0 cm^(-1) in 3, and -30.0 cm^(-1) in 4) as determined by magnetic measurements. Such findings support the idea that controlling the axial crystal field distortion is an excellent way to enhance single-ion anisotropy. High Field-High Frequency EPR measurements on 4 revealed an even higher D value, -40.0 cm^(-1). Interestingly, compound 4 exhibits evidence for an out-of-phase ac signal under dc field. In another effort, a new series of vanadium cyanide building blocks, PPN[V(acac)_(2)(CN)_(2)]∙PPNCl (13) (acac = acetylacetonate), A[V(L)(CN)_(2)] (A^(+) = Et_(4)N^(+), L = N,N'-Ethylenebis(salicylimine) (14), A = PPN^(+), L = N,N'-Ethylenebis(salicylimine) (15), L = N,N'-Phenylenebis(salicylimine) (16), and L = N,N'-Ethylenebis(2-methoxysalicylimine) (17)) were synthesized. Magnetic studies revealed moderate Dz values (-10.0, 5.89, 3.7, 4.05 and 4.36 cm^(-1) for 13-17 respectively). The first family of cyanide-bridged lanthanide containing molecules with a trigonal bipyramidal (TBP) geometry, (Et_(4)N)_(2)[(Re(triphos)(CN)_(3))_(2)(Ln(NO_(3))_(3))_(3)]-∙4CH_(3)CN (19-27 with Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy and Ho) were prepared using the [(triphos)Re(CN)_(3)]^(-) building block, results that add valuable information to our database of compounds with a TBP geometry. Magnetic studies revealed diverse magnetic responses including slow relaxation of the magnetization at zero field for 25 and 26 , an indication of SMM behavior.

This thesis details the synthesis and coordination chemistry of twenty-five nitrogencontaining heterocyclic ligands, nineteen of which were previously unreported compounds. These ligands were designed for use as synthons for the formation of molecular cages, so contain multiple coordination sites capable of bridging multiple metal atoms. The majority of molecular cages in the literature are formed by rigid bridging ligands, whereas the ligands studied in this research incorporate a higher level of flexibility, thereby lessening the degree of control over the self-assembly process and increasing the number of possible structures that can be formed upon reaction of these ligands with meal salts. Three of the new ligands synthesised were two-armed bridging ligands, which were reacted with a wide variety of metal salts to investigate what self-assembly products were formed. The complexes characterised include a M₃L₃ cyclic trimer, a range of coordination polymers of varying dimensionality, a range of dimeric products and a series of M₄L₆ cage-like molecular squares. However, the majority of ligands studied were three-armed, potentially tripodal compounds, which were envisaged as potential components of M₃L₂ or M₆L₄ molecular cages. The products of self-assembly of these ligands with various metals salts were shown to include a variety of discrete tri- and tetranuclear complexes, a range of coordination polymers of varying dimensionality and interpenetration, and a complex M₆L₄ assembly that appears to be a collapsed coordination cage. Unfortunately some of the ligands synthesised were shown to decompose in the presence of various metal salts, a phenomenon already identified in the literature. Analogues of these decomposition products were synthesised deliberately to identify the potential of a known tridentate ligand as a metallosupramolecular synthon. ¹H NMR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis and X-ray crystallography were used to study the compounds synthesised. The crystal structures of five ligands and fifty-one complexes are discussed.

This thesis details the synthesis and coordination chemistry of twenty-five nitrogencontaining heterocyclic ligands, nineteen of which were previously unreported compounds. These ligands were designed for use as synthons for the formation of molecular cages, so contain multiple coordination sites capable of bridging multiple metal atoms. The majority of molecular cages in the literature are formed by rigid bridging ligands, whereas the ligands studied in this research incorporate a higher level of flexibility, thereby lessening the degree of control over the self-assembly process and increasing the number of possible structures that can be formed upon reaction of these ligands with meal salts. Three of the new ligands synthesised were two-armed bridging ligands, which were reacted with a wide variety of metal salts to investigate what self-assembly products were formed. The complexes characterised include a M₃L₃ cyclic trimer, a range of coordination polymers of varying dimensionality, a range of dimeric products and a series of M₄L₆ cage-like molecular squares. However, the majority of ligands studied were three-armed, potentially tripodal compounds, which were envisaged as potential components of M₃L₂ or M₆L₄ molecular cages. The products of self-assembly of these ligands with various metals salts were shown to include a variety of discrete tri- and tetranuclear complexes, a range of coordination polymers of varying dimensionality and interpenetration, and a complex M₆L₄ assembly that appears to be a collapsed coordination cage. Unfortunately some of the ligands synthesised were shown to decompose in the presence of various metal salts, a phenomenon already identified in the literature. Analogues of these decomposition products were synthesised deliberately to identify the potential of a known tridentate ligand as a metallosupramolecular synthon. ¹H NMR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis and X-ray crystallography were used to study the compounds synthesised. The crystal structures of five ligands and fifty-one complexes are discussed.

Resumo: Nas diversas atividades agropecuárias o objetivo principal é alcançar o melhor desempenho, com baixo custo e menor tempo de produção. Com o avanço tecnológico na alimentação de peixes, novos equipamentos estão sendo desenvolvidos para acelerar a produção. O objetivo deste trabalho foi avaliar o manejo alimentar, utilizando dispensadores automáticos de ração, com diferentes taxas e intervalos de alimentação em alta freqüência para tilápias na fase de engorda. Foram instalados dezoito tanques-rede (TR) de 1,0 m³, num viveiro de 2000 m² de espelho d'água. Sobre os TR foram colocados suportes metálicos para sustentar os dispensadores de ração. Foram utilizadas 93 tilápias, com peso médio de 186,57± 9,08 gramas, por TR. As taxas alimentares propostas foram de 4,0%, 3,0% e 2,0% do peso vivo em freqüência alimentar de 48 vezes, em intervalos de 30 ou 22 minutos entre cada refeição, durante o período experimental de 120 dias. Os valores médios do oxigênio dissolvido, pH e temperatura foram 3,20 mg/l; 8,03 e 25,43 ºC, respectivamente. O melhor desempenho foi alcançado por peixes alimentados com 4,0% do peso vivo, com intervalo de 22 minutos, interrompendo a alimentação por um período de seis horas durante a madrugada. / Abstract: In the diverse farming activities, the main objective is to reach optimum performance, with low cost and decreasing productive time. With technological advances in the feeding of fish, new equipment have being developed to improve production. Therefore, the objective of this work was to optimize feeding strategies, using automatic feeders, to determine optimum ration level, interval and schedule of feeding of tilapias in finishing phase. It was allocated eighteen 1m³ net-cages (NC) 1 m³, into a pond of 2000m² of water mirror. On the NCs, a metallic support was placed to support the automatic feeders. Above 93 Nile tilapia with 186,57± 9,08 g, average weight were stocked into each NC. Feeding levels were 4%, 3% and 2% of the alive weight and feeding frequency were 48 times, in intervals of 22 and 30 min, during 120 days. The average values of the dissolved oxygen, pH and temperature were 3,20 mg/l, 8,03 and 25,43ºC, respectively. The level of 4% and period of 24 hours resulted in better growth performance reaching the 683,73 g of final weight. / Orientador: Claudio Angelo Agostinho / Coorientador: Luiz Edivaldo Pezzato / Banca: Delma Machado Cantisani Pádua / Banca: Marcos Gomes Nogueira / Mestre

The aim of the thesis was comparing production parameters of laying hens breeding in different housing systems at a production enterprise, it means in enriched cages and aviary. There is used the laying hybrid ISA Brown for production consumer eggs. The achievement during 13months' cycle shown that in each laying month except 1st laying month the higher hen-day egg production was fond out by hens in enriched cages. The hen-egg production per month was higher in enriched cages too. The higher mortality was demonstrated by hens in aviary during all laying months. Both housing systems reached the highest mortality in the 13th laying month. The hens in aviary had higher feed consumption per egg during all months. Higher daily feed consumption was assigned by the hens in the aviary in the 1st, 2nd and 3rd month and from the 9th to the 13th laying month. In other laying months the hens in enriched cages had higher daily feed consumption. Feed costs formed the highest entry of total costs.

The first chapter of this thesis introduces the fundamental concepts governing the design and synthesis of supramolecular complexes. By illustrating the synthesis of several coordination cages reported in the literature, the principles underlying the construction of coordination cages by subcomponent self-assembly are elucidated. Ionic liquids are then proposed as solvents for cage systems; general methods for the preparation and synthesis of these solvents are described. The second chapter explores the use of ionic liquids as solvents for existing coordination cages. Potential methods of characterising these cages in ionic liquids are discussed; cages are demonstrated to be stable and capable of encapsulating guests in these ionic environments; and systems in which cages have good solubility in ionic liquids are designed. Building upon these observations, a triphasic sorting system is presented such that each of three different host-guest complexes are soluble in only one of three immiscible liquid phases. In contrast to the static triphasic system described in the second chapter, the third chapter explores directed phase transfer of coordination cages and their cargos from water, across a phase interface, and into an ionic liquid phase. The host-guest complex can then be recycled from the ionic liquid layer back into water after several additional steps. Furthermore, phase transfer of cationic cages is used to separate a mixture of cationic and anionic host-guest complexes. In the fourth chapter, fully reversible phase transfer of coordination cages is developed. Using anion exchange to modulate the solubility of three different cationic cages, reversible transport between water and ethyl acetate is demonstrated. Sequential phase transfer can also be achieved such that, from a mixture of cubic (+16) and tetrahedral (+8) cages, the cubic cage transfers from water to ethyl acetate before the tetrahedral cage. This process is fully reversible; upon the addition of a hydrophilic anion, the tetrahedral cage returns from ethyl acetate to water before the cubic cage.

Made available in DSpace on 2016-08-17T18:39:44Z (GMT). No. of bitstreams: 1 4573.pdf: 2386349 bytes, checksum: 7ed71a71bbb8a21974731217325807a0 (MD5) Previous issue date: 2011-12-13 / Financiadora de Estudos e Projetos / With the increased interest in growing native fish species the tetra has been highlighted nationally in the marketing of fish facing the two niche markets: as a snack in bars and restaurants and other natural bait for sport fishing. Therefore, studies on the stocking density are needed for better understanding in response to performance than can affect the growth, nutrition and animal behavior. This study aimed to evaluate the economic viability and growth performance of the tetra (Astyanax altiparanae) in cages, subjected to different stocking rates. The experiment was conducted on the premises of the UPD Pirassununga, APTA Pole Central East, in cages of 1m3, villages in densities: 250,450 and 600 fish per tank with 4 repetitions. The temperature, water clarity, dissolved oxygen an pH were daily measured. The tetra were fed extruded commercial diet containing 36%of protein. The experiment lasted 57 days and monthly samples were collected to evaluate the development and adjust amount of feed. To verify the significance between treatment means was used Tukey s test at 5% probability. The results showed increasing linear effect for variable total biomass (p<0,05) as opposed to the linear effect (p<0,05) for average consumption of feed as well as weight gain, average final length and final weight medium according to the increase of stocking density. The physic-chemical parameters remained at adequate levels. It is concluded that stocking density affects the development of juveniles of tetra and the density of persons over fishes/m³. Can still be used in the cultivation of 600 fishes/m³ tetra juveniles in cages, resulting in higher total biomass, although they result in smaller populations. / Com o aumento do interesse no cultivo de espécies de peixes nativos, o lambari tem se destacado nacionalmente na comercialização de pescado frente à dois nichos de mercado: um como petiscos em bares e restaurantes e outro como isca natural para a pesca esportiva. Sendo assim, estudos referentes à densidade de estocagem se fazem necessários para um melhor entendimento frente ao desempenho produtivo que pode afetar o crescimento, a alimentação e o comportamento dos animais. Neste estudo, objetivou-se avaliar a viabilidade econômica e o desempenho produtivo do lambari (Astianax altiparanae) em tanquesrede, submetidos à diferentes densidades de estocagem. O experimento foi conduzido nas instalações da UPD de Pirassununga, Pólo APTA Centro-Leste, em tanques-redes de 1m3, povoados nas densidades de: 250, 400 e 600 peixes por tanque com 4 repetições. A temperatura, transparência da água, oxigênio dissolvido e o pH foram aferidos diariamente.Os lambaris foram alimentados com ração comercial extrusada contendo 36% de proteína bruta. O experimento durou 57 dias e mensalmente foram realizadas biometrias para avaliar o desenvolvimento e o ajuste da quantidade de ração. Para verificar a significância entre as médias dos tratamentos foi utilizado o teste de Tukey, ao nível de 5% de probabilidade. Os resultados mostraram efeito linear crescente para variável de biomassa total (p<0,05) em oposição ao efeito linear decrescente (p<0,05) para consumo médio de ração, assim como ganho de peso médio, comprimento final médio e peso final médio conforme aumento da densidade de estocagem. Os parâmetros físicoquímicos permaneceram em níveis adequados. Conclui-se que a densidade de estocagem afeta o desenvolvimento dos juvenis de lambari e que a densidade de 300 peixes/m3proporciona indivíduos maiores. Ainda pode-se utilizar 600 peixes/m3 no cultivo de juvenis de lambari em tanque-rede, resultando em maior biomassa total, apesar de resultarem em populações menores.

Resumo: Com o intuito de conhecer o potencial zootécnico do pampo, foi avaliado o efeito de diferentes densidades de estocagem (100 e 200 peixes/m3) na sobrevivência e crescimento do pampo amarelo (Trachinotus carolinus), criado em tanque-rede instalado em ambiente marinho. Peixes com aproximadamente 1,0 a 2,0 g, capturados em arrastos nas praias rasas do município de Ubatuba, SP, foram transportados ao Núcleo de Pesquisa e Desenvolvimento do Litoral Norte - Agência Paulista Tecnológica do Agronegócio - Secretaria da Agricultura e Abastecimento e mantidos durante 45 dias em tanques-rede de 5mm de malhagem. Após seleção manual, animais de 4,0 ± 0,17g foram estocados, nas densidades de 100 e 200 peixes/m3, em tanques-rede de multifilamento com 2 x 2 x 1,5m e 12 mm de malhagem, fixos a um "deck" flutuante (6,0 x 8,0 m), instalado diretamente no mar a profundidade de aproximadamente 3,5 ± 0,5 m. Os animais foram alimentados duas vezes ao dia até a saciação com ração de 40% de PB. Após 120 dias, as taxas de sobrevivência média observadas foram 77,23% e 73,11 %; pesos médios (52,79 ± 4.86 9 e 52,64 ± 5.64 g); Ganho de Peso (GP) (48,69 ± 4,05 9 e 48,73 ± 4,00 g); Taxa de Crescimento Especifico (TCE) (2,13 ± 1,24 e 2,16 ± 1,03) e Conversão Alimentar Aparente (CAA) (3,23 ± 1,52 e 2,66 ± 0,78), respectivamente para 100 e 200 peixes/m3. Estes dados não apresentaram diferenças significativas (P~0,05) entre os tratamentos testados. Entretanto os ganhos de peso do pampo, no presente experimento foram superiores a muitos trabalhos encontrados na literatura, o que nos leva a concluir que a densidade de 200 peixes/m3, utilizada neste estudo, pode ainda estar abaixo da capacidade de suporte para a espécie e pode ser o ponto de partida para futuros estudos, considerando o estágio de desenvolvimento dos animais. / Abstract: Aiming to know the zoothecnic potential of pampo, it was evaluated the effect of stocking densities (100 and 200 fish/m3) in the survival and growth rates of Florida pampano (Trachinotus carolinus), reared in marine cage. Fish with approximately 1 - 2g captured by seine in flat beaches of the city of Ubatuba, S.P. were transferred to the Núcleo de Pesquisa e Desenvolvimento do Litoral Norte - Agencia Paulista Tecnologica do Agronegocio - Secretaria Agricultura e Abastecimento and kept during 45 days in cage of 5mm mesh size. After manual selection, animals of 4.0 ± 0.17g had been stored, in the studied densities, cage of multifilament with 2 x 2 x 1.5 m and 12 mm of mesh size fixed to a"deck" (6.0 8.0 m), installed directly in the sea at a depth of approximately 3.5 ± 0.5 m. The animals had been fed twice¬-a day until satiation with ration of 40% of PB. Soon after a 120 days experimental period, the average survival rate (77.23% and 73.11 %); average body-weight (52.79 ± 4.86 and 52.64 ± 5.64); weiht gain (48.69 ± 4.05 and 48.73 ± 4.00); daily growth increment (2.13 ± 1.24 and 2.16±1.03) and apparent feed conversion rate (3.23 ± 1.52 and 2.66 ± 0.78), respectively for 100 and 200 fish/m3,were recorded. These parameters didn't present significant differences (P>=0,05) between the tested treatments. However pampo weight gain, in this experiment have been superior to many works found in literature, what allows the conclusion that pampo can be reaise in sea cages in densities above 200 fish/m3, and this density could be the starting point for future studies. / Orientador: Newton Castagnolli / Coorientador: Sérgio Ostini / Banca: João Donato Scorvo Filho / Banca: João Batista Kochenborger Fernandes / Mestre

Orientador: Dalton José Carneiro / Banca: Margarida Maria Bastos / Banca: Claudinei da Cruz / Banca: Rosângela Kiyoko Jomori / Banca: Rodrigo Roubach / Resumo: O estudo teve como objetivo comparar o desempenho produtivo de tilápias do Nilo revertidas ou não por meio da utilização do hormônio 17-α-metiltestosterona (MT) adicionado a dietas práticas e analisar histologicamente o fígado dos peixes. Foram conduzidos quatro experimentos com tilápias do Nilo, da linhagem tailandesa, revertidas ou não revertidas, desde a larvicultura até a engorda em tanques-rede. As dietas utilizadas nos experimentos foram formuladas de forma a assemelharem-se às dietas comerciais utilizadas nas pisciculturas, sendo isocalóricas, variando os níveis e fontes de proteína bruta. Procurou-se simular as causas de fígado gorduroso e friável e mortalidade próxima ao abate de tilápias do Nilo cultivadas em regime intensivo. No primeiro experimento, conduzido com larvas desde a eclosão até 60 dias de idade, observou-se que o nível de 30 mgMT.kg-1 adicionado à dieta, possibilitou eficiência na reversão, melhor desempenho produtivo e menores danos ao fígado que na dosagem de 60 mgMT.kg-1. Nesse mesmo experimento, os peixes que não receberam hormônio tiveram maior taxa de sobrevivência e não mostraram alterações histológicas no fígado. No segundo experimento, a reversão sexual favoreceu o desempenho dos juvenis na fase de recria. Porém, não foi possível observar diferenças no desempenho entre os níveis de proteína da dieta. Um terceiro experimento com tilápias cultivadas em tanques-rede dos 120 aos 600 g de peso, os peixes mostraram melhor desempenho quando alimentados com dieta contendo 32% PB, sendo que o fato de terem passado pelo processo de reversão ou não, não influenciou o desempenho. Um quarto experimento foi realizado concomitantemente ao terceiro em laboratório com juvenis de 30 g até atingirem 200 g e as tilápias revertidas apresentaram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of the study was compared reversed or no reversed Nile tilapia growth performance and liver histology. Fishes were sex reversed with addition of 17-α- methyltestosterone (MT) at the diets. The study was divided in four experiments: larval phase, growth phase and the final phases in cages and at laboratory. The diets were isocalorics, formulated as commercials diets common used in the Brazil tilapia cultures, utilizing levels and sources protein. The objective was simulated the fat liver problem detected at tilapia farms. In the first experiment, there were used fries until 60 days of culture. There was observed that the level of 30 mgMT.kg-1 conducted to efficiency in the sex reversal with best growth performance and less liver damages than the level of 60 mgMT.kg-1. The fishes that didn't receive MT reached best survival and didn't show any liver alteration. In the second experiment, the facts of the fishes were sex reversed increased the growth performance of juveniles. But there was not difference in the growth performance by protein levels. The third experiment conducted at cages, with fishes of 120g until 600g, showed best growth performance when fed with 32% crude protein, but there was no difference by the fact of they were reversed or no. The fourth experiment was conducted at the same time of the third, at laboratory with tilapias of 30g until 200g. The reversed fishes showed best growth performance than the no reversed ones. Alterations of liver histology of the fishes reversed at the four experiments were noted. But there were more severe in the fishes fed with higher levels of crude protein. / Doutor

Production, egg quality, behaviour, and physical condition were compared from Wk 20 to Wk 50 among three beak- trimmed commercial laying strains, Lohmann White (LW), H & N White (HN), Lohmann Brown (LB), and a non-commercial Cross between Rhode Island Red (male) and Barred Plymouth Rock (female) in conventional cages and in floor pens. All chicks were reared in their respective environments, and 450 and 432 pullets were housed at 18 and 7 weeks of age in cages and floor pens respectively. Hens in cages were provided with 688 cm2/bird and those in pens with over 6,000 cm2/bird, both of which are more than provided by commercial standards. Body weights and eggshell weights were higher for birds in floor pens than those in cages, and although they increased with age, body weight of hens in cages decreased at Wk 50. White-egg layers (LW, HN) used perches and nest boxes more than Brown-egg layers (LB, Cross). During the laying period, mortality was higher for all strains in cages and during the rearing period mortality was higher in floor pens for LB hens but not other strains. No aggressive behaviours were found, but the frequency of gentle feather pecking and pecking at the enclosure was higher in cages than in floor pens. Feather condition deteriorated over time in cages mainly because of contact with the cage wires whereas in floor pens, feather condition of birds at Wk 20 was not different from that at Wk 50. The frequency of keel bone deformities was higher for White-egg layers than for Brown-egg layers in cages and was higher for Cross hens than other strains in floor pens. Claws were longer in cages than in the floor pens. Foot condition was worse in floor pens than in cages. The welfare indicators used in this study showed that cages restricted the hens' behaviour compared to floor pens and resulted in higher laying period mortality, reduced body weight and deteriorated feather condition than floor pens. Both systems had advantages and disadvantages in regard to the hens’ health and welfare. The use of environmental complexities was strain specific in floor pens. The environment by genotype interactions suggests that the strain should be considered when considering alternative housing systems. / Land and Food Systems, Faculty of / Graduate