O produto formado a partir da reação entre trans-[Ru(NH3)4P(OEt) 3H2O]2+ e íons nitrito é dependente da concentração hidrogeniônica do meio. Em pH acima de 10, o composto final formado é o trans-[Ru(NH3)4P(OEt) 3NO2]+ (1,1 x 103 M-1.s-1), o qual é convertido quantitativamente em pH 4 ao correspondente nitrosilo (2,2 x 10-3 s-1). Esta reação em meio alcalino ocorre em duas etapas com constantes de velocidades distintas, sendo a primeira etapa mais rápida que a segunda. Esta etapa foi atribuída à formação dos isômeros, trans-[Ru(NH3)4P(OEt) 3NO2]+ e trans-[Ru(NH3)4P(OEt) 3ONO] + (1,1 x 103 M-1 s-1; pH 11). A etapa mais lenta foi atribuída à isomerização do nitrito composto, nitrito ligado pelo oxigênio, para o nitro composto, ligado pelo nitrogênio e que apresenta maior estabilidade (6,9 x 102 M-1 s-1; pH 11). Através de estudos in vitro foi efetuada a avaliação da citotoxicidade de nitrosilos complexos de rutênio tipo trans-[Ru(NO)(NH3)4L] 3+ e trans-[Ru(NH3)4L(SO4)]+ em culturas de células de diferentes modelos de câncer. Verificou-se que estes compostos apresentaram resultados efetivos em células de leucemia Humana (Jurkat) e Melanoma Murino (B16F10-Nex2). Os compostos acima também se mostraram citotóxicos frente a células de câncer de Mama Humana (MCF-7). Estudos in vivo com células B16F10-Nex2 envolvendo nitrosilo complexos e seus análogos sulfatos indicaram que a aplicação intraperitoneal destes compostos retardou o desenvolvimento dos tumores e aumentou a sobrevida dos camundongos. Os resultados também indicam que a morte celular promovida pelos complexos provavelmente não é dependente de caspases. A aplicação dos nitrosilos, SNP e [Ru(NO)Hedta], em culturas celulares embriogênicas de Araucaria angustifolia induziram um aumento na massa fresca das culturas em relação ao controle, após 21 dias. Este efeito foi inibido quando PTIO, captador de NO, foi adicionado às amostras em conjunto com os doadores de NO. Observou-se também, que após 21 dias, as amostras preparadas com os compostos apresentaram maior concentração de óxido nítrico, tanto intra quanto extracelular. As morfologias das células também foram influenciadas pela adição dos nitrosilos, observando-se um acréscimo no número de células embriogênicas em relação ao controle, acréscimo este que ocorreu ocorre de forma desorganizada. / The product of the reaction of trans-[Ru(NH3)4P(OEt) 3H2O]2+ with nitrite ions depends on the hydrogenionic concentration of the medium. In solutions with pH > 10, the final compound is the trans-[Ru(NH3)4P(OEt) 3NO2]+ (1,1 x 103 M-1.s-1), wich is quantitatively converted into the trans-[Ru(NH3)4P(OEt) 3NO]3+ in acid solutions (CH+ > 10-5 mol.L-1; kobs = 2.2 x 10-3 s-1 at pH 4). This reaction presents two different steps with distinct rate constants, being the first step faster than the second. Then, the first process was attributed to the formation of both the isomers, trans-[Ru(NH3)4P(OEt)3NO2]+ and trans-[Ru(NH3)4P(OEt)3ONO]+ (1.1 x 103 M-1s-1; pH 11). The slowest step was then attributed to the isomerization of the nitrito compound, O-bonded, to the nitro compound, Nbonded, which presents more stability (6.9 x 102 M-1s-1; pH 11). In vitro studies were used to evaluate the cytotoxicity of some nitrosyl ruthenium compounds type trans-[Ru(NO)(NH3)4L]3+ and trans-[Ru(NH3)4L(SO4)]+ against some cancer cells models. The compounds showed significant results against human leukemia (Jurkat) and murine melanoma (B16F10-Nex2). The compounds also showed citotoxicity against human breast adenocarcinoma cell line (MCF-7), however the compounds were less active in this culture. In vivo studies with B16F10-Nex2 and the ruthenium compounds suggests that intraperitoneally applications of the complexes delays tumor growth and prolongs animal survival rate. The results also indicates that the compounds should induce a caspase-independent death of the tumor cell. The application of the nitrosyls, SNP and [Ru(NO)Hedta], in embryogenic suspension cultures of Araucaria angustifolia promotes an increase at the fresh mass percent comparing with the control samples. This effect was inhibit when the compound PTIO, a NO scavenger, was added to the samples prepared with NO donors. After 21 days of cellular culture, fluorimetric methods for NO detection showed that the samples prepared with SNP and [Ru(NO)Hedta] presents higher intra and extracellular NO concentrations than control. Morphological organization of embryogenic suspension cultures of A. angustifolia were also influenced by the addition of NO, the cultures with the donors showed increased embriogenic cells numbers relating to the control.

Phytophthora cinnamomi has been recognised as a key threatening process to Australia’s biodiversity by the Commonwealth’s Environment Protection and Biodiversity Conservation Act 1999. Despite over 80 years of extensive research, its exact mode of survival is still poorly understood. It is widely accepted that thin- and thick-walled chlamydospores are the main survival propagules while oospores are assumed to play no role in the survival of the pathogen in the Australian environment, yet evidence is limited. The saprophytic ability of the pathogen is still unresolved despite the important role this could play in the ability of the pathogen to survive in the absence of susceptible hosts. This thesis aimed to investigate chlamydospores, oospores and the saprophytic ability of P. cinnamomi to determine their contribution to survival. Phytophthora cinnamomi did not show saprophytic ability in non-sterile soils. The production of thick-walled chlamydospores and selfed oospores of P. cinnamomi in vitro was documented. Thick-walled chlamydospores were sporadically formed under sterile and non-sterile conditions in vitro but exact conditions for stimulating their formation could not be determined. The formation of thick-walled chlamydospores emerging from mycelium of similar wall thickness was observed, challenging the current knowledge of chlamydospore formation. Selfed oospores were abundant in vitro on modified Ribeiro’s minimal medium in one isolate. Three other isolates tested also produced oospores but not in large numbers. Although the selfed oospores did not germinate on a range of media, at least 16 % were found to be viable using Thiozolyl Blue Tetrazolium Bromide staining and staining of the nuclei with 4´, 6-diamidino-2-phenylindole.2HCl (DAPI). This indicated the potential of selfed oospores as survival structures and their ability to exist dormantly. The ability of phosphite to kill chlamydospores and selfed oospores was studied in vitro. Results challenged the efficacy of this chemical and revealed the necessity for further study of its effect on survival propagules of P. cinnamomi in the natural environment. Phosphite was shown to induce dormancy in thin-walled chlamydospores if present during their formation in vitro. Interestingly, dormancy was only induced by phosphite in isolates previously reported as sensitive to phosphite and not those reported as tolerant. Chlamydospores were produced uniformly across the radius of the colony on control modified Ribeiro’s minimal medium but on medium containing phosphite (40 or 100 µg ml-1), chlamydospore production was initially inhibited before being stimulated during the log phase of growth. This corresponded to a point in the colony morphology where mycelial density changed from tightly packed mycelium to sparse on medium containing phosphite. This change in morphology did not occur when the pathogen was grown on liquid media refreshed every four days, and chlamydospores were evenly distributed across the radius of these colonies. This trend was not observed in selfed oospores produced in the presence of phosphite. Selfed oospore production was found to be inhibited by phosphite at the same concentrations that stimulated chlamydospore production. Isolates of P. cinnamomi were transformed using a protoplast/ polyethylene glycol method to contain the Green Fluorescent Protein and geneticin resistance genes to aid in future studies on survival properties of the organism. Although time constraints meant the stability of the transgene could not be determined, it was effective in differentiating propagules of the transformed P. cinnamomi from spores of other microrganisms in a non-sterile environment. Two different sized chlamydospores (approximately 30 µm diameter and < 20 µm diameter) were observed in preliminary trials of transformed P. cinnamomi inoculated lupin roots floated in non-sterile soil extracts and these were easily distinguished from microbial propagules of other species. The growth and pathogenicity was reduced in two putative transformants and their ability to fluoresce declined over ten subcultures but they still remained resistant to geneticin. This study has improved our knowledge on the survival abilities of P. cinnamomi in vitro and has provided a useful tool for studying these abilities under more natural glasshouse conditions. Important implications of phosphite as a control have been raised.

Made available in DSpace on 2014-06-11T19:28:36Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-25Bitstream added on 2014-06-13T19:58:11Z : No. of bitstreams: 1 gomes_glgc_me_botfca.pdf: 1828548 bytes, checksum: 5ea149ea43e1fae2645b977340ddc416 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O glyphosate é um herbicida de largo espectro de controle, não seletivo, e seu sítio de ação é a inibição da enzima 5-enolpiruvilchiquimato 3-fosfato sintase (EPSPs). Com a inibição da enzima, e o bloqueio da rota do ácido chiquímico pelo glyphosate, ocorre o acúmulo de alguns compostos como os ácidos chiquímico e quínico, além de outras alterações metabólicas e fisiológicas nas plantas. O objetivo deste trabalho foi avaliar as alterações metabólicas e fisiológicas de plantas de milho submetidas à aplicação de glyphosate isolado e em associação com fosfito. O experimento foi conduzido em casa-de-vegetação, no Núcleo de Pesquisas Avançadas em Matologia (NUPAM), pertencente à Faculdade de Ciências Agronômicas – FCA/UNESP. Foi utilizado o híbrido de milho Pioneer 30F53, em vasos contendo 5 litros de substrato e os tratamentos foram compostos da aplicação de: glyphosate (72 g e.a. ha-1); glyphosate (720 g e.a. ha-1); glyphosate (72 g e.a. ha-1) + fosfito (3 L p.c. ha-1); glyphosate (720 g e.a. ha-1) + fosfito (3 L p.c. ha-1); fosfito (3 L p.c. ha-1); e uma testemunha sem aplicação. Foram realizados dois experimentos, com os mesmos tratamentos, mas com avaliações distintas. No primeiro, foram realizadas cinco coletas de todas as folhas das plantas aos 2, 4, 6, 10 e 15 dias após a aplicação (DAA) dos tratamentos. No segundo experimento, foi realizada a medição do fluxo de transporte de elétrons (ETR) nas folhas jovens e maduras, avaliações visuais de intoxicação, medição da altura e quantificação da matéria seca ao final do experimento. As folhas coletadas foram secas e moídas e utilizadas para quantificação dos seguintes compostos: ácido chiquímico, ácido quínico, ácido desidrochiquímico, ácido aminometilfosfônico (AMPA), glyphosate, fenilalanina, tirosina e triptofano. Foram também realizados testes de extração dos compostos... / The glyphosate is a broad spectrum herbicide, non-selective, and the site of action is the inhibition of the enzyme 5-enolpyruvylshikimate 3-phosphate synthase (EPSPs). The inhibition of the enzyme results in a reduction in the synthesis of aromatic amino acids (phenylalanine, tyrosine and tryptophan), and secondary compounds. The glyphosate block of the shikimic acid pathway and causes the accumulation of some compounds like shikimic acid and quinic acid, and other metabolic and physiological effects in plants. The objective of this study was to evaluate the metabolic and physiological effects in corn plants after application of glyphosate and phosphite. The experiment was carried out in greenhouse in the Faculty of Agronomic Sciences at São Paulo State University. It was used the corn Pioneer 30F53, planted in vases containing 5 liters of substrate. The treatments were: glyphosate (72 g a.e. ha 1), glyphosate (720 g a.e. ha-1), glyphosate (72 g a.e. ha-1) + phosphite (3 L ha-1), glyphosate (720 g a.e. ha-1) + phosphite (3 L ha-1), phosphite (3 L ha -1) and an untreated control. Two experiments were carried out with the same treatments but with different evaluations. At first, it were realized five samples of all corn plant leaves at 2, 4, 6, 10 and 15 days after application (DAA). The second experiment was performed the evaluation of the electron transport rate (ETR) in young and mature leaves, visual evaluations of intoxication, height and weight of the plants. The leaves collected were dried, grated and used to quantify the compounds: shikimic acid, quinic acid, 3-dehydroshikimic acid, aminomethylphosphonic acid (AMPA), glyphosate, phenylalanine, tyrosine and tryptophan. Extraction tests of compounds were conducted to choose the most appropriate and were development of analytical methods in LC-MS/MS. The extraction of the compounds that proved most appropriate was using the dry mass... (Complete abstract click electronic access below)

Resumo: O glyphosate é um herbicida de largo espectro de controle, não seletivo, e seu sítio de ação é a inibição da enzima 5-enolpiruvilchiquimato 3-fosfato sintase (EPSPs). Com a inibição da enzima, e o bloqueio da rota do ácido chiquímico pelo glyphosate, ocorre o acúmulo de alguns compostos como os ácidos chiquímico e quínico, além de outras alterações metabólicas e fisiológicas nas plantas. O objetivo deste trabalho foi avaliar as alterações metabólicas e fisiológicas de plantas de milho submetidas à aplicação de glyphosate isolado e em associação com fosfito. O experimento foi conduzido em casa-de-vegetação, no Núcleo de Pesquisas Avançadas em Matologia (NUPAM), pertencente à Faculdade de Ciências Agronômicas - FCA/UNESP. Foi utilizado o híbrido de milho Pioneer 30F53, em vasos contendo 5 litros de substrato e os tratamentos foram compostos da aplicação de: glyphosate (72 g e.a. ha-1); glyphosate (720 g e.a. ha-1); glyphosate (72 g e.a. ha-1) + fosfito (3 L p.c. ha-1); glyphosate (720 g e.a. ha-1) + fosfito (3 L p.c. ha-1); fosfito (3 L p.c. ha-1); e uma testemunha sem aplicação. Foram realizados dois experimentos, com os mesmos tratamentos, mas com avaliações distintas. No primeiro, foram realizadas cinco coletas de todas as folhas das plantas aos 2, 4, 6, 10 e 15 dias após a aplicação (DAA) dos tratamentos. No segundo experimento, foi realizada a medição do fluxo de transporte de elétrons (ETR) nas folhas jovens e maduras, avaliações visuais de intoxicação, medição da altura e quantificação da matéria seca ao final do experimento. As folhas coletadas foram secas e moídas e utilizadas para quantificação dos seguintes compostos: ácido chiquímico, ácido quínico, ácido desidrochiquímico, ácido aminometilfosfônico (AMPA), glyphosate, fenilalanina, tirosina e triptofano. Foram também realizados testes de extração dos compostos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The glyphosate is a broad spectrum herbicide, non-selective, and the site of action is the inhibition of the enzyme 5-enolpyruvylshikimate 3-phosphate synthase (EPSPs). The inhibition of the enzyme results in a reduction in the synthesis of aromatic amino acids (phenylalanine, tyrosine and tryptophan), and secondary compounds. The glyphosate block of the shikimic acid pathway and causes the accumulation of some compounds like shikimic acid and quinic acid, and other metabolic and physiological effects in plants. The objective of this study was to evaluate the metabolic and physiological effects in corn plants after application of glyphosate and phosphite. The experiment was carried out in greenhouse in the Faculty of Agronomic Sciences at São Paulo State University. It was used the corn Pioneer 30F53, planted in vases containing 5 liters of substrate. The treatments were: glyphosate (72 g a.e. ha 1), glyphosate (720 g a.e. ha-1), glyphosate (72 g a.e. ha-1) + phosphite (3 L ha-1), glyphosate (720 g a.e. ha-1) + phosphite (3 L ha-1), phosphite (3 L ha -1) and an untreated control. Two experiments were carried out with the same treatments but with different evaluations. At first, it were realized five samples of all corn plant leaves at 2, 4, 6, 10 and 15 days after application (DAA). The second experiment was performed the evaluation of the electron transport rate (ETR) in young and mature leaves, visual evaluations of intoxication, height and weight of the plants. The leaves collected were dried, grated and used to quantify the compounds: shikimic acid, quinic acid, 3-dehydroshikimic acid, aminomethylphosphonic acid (AMPA), glyphosate, phenylalanine, tyrosine and tryptophan. Extraction tests of compounds were conducted to choose the most appropriate and were development of analytical methods in LC-MS/MS. The extraction of the compounds that proved most appropriate was using the dry mass... (Complete abstract click electronic access below) / Orientador: Edivaldo Domingues Velini / Coorientador: Maria Lúcia Bueno Trindade / Banca: João Domingos Rodrigues / Banca: Marcus Barifouse Matallo / Mestre

O produto formado a partir da reação entre trans-[Ru(NH3)4P(OEt) 3H2O]2+ e íons nitrito é dependente da concentração hidrogeniônica do meio. Em pH acima de 10, o composto final formado é o trans-[Ru(NH3)4P(OEt) 3NO2]+ (1,1 x 103 M-1.s-1), o qual é convertido quantitativamente em pH 4 ao correspondente nitrosilo (2,2 x 10-3 s-1). Esta reação em meio alcalino ocorre em duas etapas com constantes de velocidades distintas, sendo a primeira etapa mais rápida que a segunda. Esta etapa foi atribuída à formação dos isômeros, trans-[Ru(NH3)4P(OEt) 3NO2]+ e trans-[Ru(NH3)4P(OEt) 3ONO] + (1,1 x 103 M-1 s-1; pH 11). A etapa mais lenta foi atribuída à isomerização do nitrito composto, nitrito ligado pelo oxigênio, para o nitro composto, ligado pelo nitrogênio e que apresenta maior estabilidade (6,9 x 102 M-1 s-1; pH 11). Através de estudos in vitro foi efetuada a avaliação da citotoxicidade de nitrosilos complexos de rutênio tipo trans-[Ru(NO)(NH3)4L] 3+ e trans-[Ru(NH3)4L(SO4)]+ em culturas de células de diferentes modelos de câncer. Verificou-se que estes compostos apresentaram resultados efetivos em células de leucemia Humana (Jurkat) e Melanoma Murino (B16F10-Nex2). Os compostos acima também se mostraram citotóxicos frente a células de câncer de Mama Humana (MCF-7). Estudos in vivo com células B16F10-Nex2 envolvendo nitrosilo complexos e seus análogos sulfatos indicaram que a aplicação intraperitoneal destes compostos retardou o desenvolvimento dos tumores e aumentou a sobrevida dos camundongos. Os resultados também indicam que a morte celular promovida pelos complexos provavelmente não é dependente de caspases. A aplicação dos nitrosilos, SNP e [Ru(NO)Hedta], em culturas celulares embriogênicas de Araucaria angustifolia induziram um aumento na massa fresca das culturas em relação ao controle, após 21 dias. Este efeito foi inibido quando PTIO, captador de NO, foi adicionado às amostras em conjunto com os doadores de NO. Observou-se também, que após 21 dias, as amostras preparadas com os compostos apresentaram maior concentração de óxido nítrico, tanto intra quanto extracelular. As morfologias das células também foram influenciadas pela adição dos nitrosilos, observando-se um acréscimo no número de células embriogênicas em relação ao controle, acréscimo este que ocorreu ocorre de forma desorganizada. / The product of the reaction of trans-[Ru(NH3)4P(OEt) 3H2O]2+ with nitrite ions depends on the hydrogenionic concentration of the medium. In solutions with pH &gt; 10, the final compound is the trans-[Ru(NH3)4P(OEt) 3NO2]+ (1,1 x 103 M-1.s-1), wich is quantitatively converted into the trans-[Ru(NH3)4P(OEt) 3NO]3+ in acid solutions (CH+ &gt; 10-5 mol.L-1; kobs = 2.2 x 10-3 s-1 at pH 4). This reaction presents two different steps with distinct rate constants, being the first step faster than the second. Then, the first process was attributed to the formation of both the isomers, trans-[Ru(NH3)4P(OEt)3NO2]+ and trans-[Ru(NH3)4P(OEt)3ONO]+ (1.1 x 103 M-1s-1; pH 11). The slowest step was then attributed to the isomerization of the nitrito compound, O-bonded, to the nitro compound, Nbonded, which presents more stability (6.9 x 102 M-1s-1; pH 11). In vitro studies were used to evaluate the cytotoxicity of some nitrosyl ruthenium compounds type trans-[Ru(NO)(NH3)4L]3+ and trans-[Ru(NH3)4L(SO4)]+ against some cancer cells models. The compounds showed significant results against human leukemia (Jurkat) and murine melanoma (B16F10-Nex2). The compounds also showed citotoxicity against human breast adenocarcinoma cell line (MCF-7), however the compounds were less active in this culture. In vivo studies with B16F10-Nex2 and the ruthenium compounds suggests that intraperitoneally applications of the complexes delays tumor growth and prolongs animal survival rate. The results also indicates that the compounds should induce a caspase-independent death of the tumor cell. The application of the nitrosyls, SNP and [Ru(NO)Hedta], in embryogenic suspension cultures of Araucaria angustifolia promotes an increase at the fresh mass percent comparing with the control samples. This effect was inhibit when the compound PTIO, a NO scavenger, was added to the samples prepared with NO donors. After 21 days of cellular culture, fluorimetric methods for NO detection showed that the samples prepared with SNP and [Ru(NO)Hedta] presents higher intra and extracellular NO concentrations than control. Morphological organization of embryogenic suspension cultures of A. angustifolia were also influenced by the addition of NO, the cultures with the donors showed increased embriogenic cells numbers relating to the control.

Submitted by THIAGO TASSIO DE SOUSA SILVA null (thiago_tassio.ef@hotmail.com) on 2017-08-22T22:00:09Z No. of bitstreams: 1 20.pdf: 1468120 bytes, checksum: cdc42b128dc74d02bfda2b7ce03783f0 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-08-23T18:23:37Z (GMT) No. of bitstreams: 1 silva_tts_me_bot.pdf: 1468120 bytes, checksum: cdc42b128dc74d02bfda2b7ce03783f0 (MD5) / Made available in DSpace on 2017-08-23T18:23:37Z (GMT). No. of bitstreams: 1 silva_tts_me_bot.pdf: 1468120 bytes, checksum: cdc42b128dc74d02bfda2b7ce03783f0 (MD5) Previous issue date: 2016-08-05 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O setor florestal é um dos que mais contribui em termos sociais, econômicos e ambientais para o Brasil. Dentro deste setor, a eucaliptocultura pode ser apontada como a mais importante do segmento, com o plantio que representa 5,56 milhões de hectares. A primeira etapa do processo de implantação de florestas de eucaliptos é a produção de mudas, que no Brasil é feita por meio da clonagem, garantindo qualidade das mudas plantada no viveiro Porém, um dos principais desafios em viveiros, é o controle de patógenos, entre eles, Oidium eucalypti Rostrup., que apresenta maior incidência e se destaca devido à severidade e danos causados, e também à variedade de espécies e híbridos de eucalipto que são suscetíveis a doença. Pressupõe a hipótese que a utilização do fosfito e silício diminui o nível de severidade de bacteriose, e mantém a uniformidade da qualidade de mudas em viveiros florestais. Portanto, para testar estas hipóteses, objetivou-se com este trabalho avaliar o efeito da aplicação de produtos contendo fosfito e silício no controle de bacteriose, e na qualidade de mudas de Eucalyptus urograndis em um viveiro comercial. O delineamento experimental foi inteiramente casualizado, com quatro repetições e dez tratamentos (Zincazot, Fitofos-Cu, Fitofos-K, Fitofos-Zn-Mn, Silamol, Amorux, Fitofos-Cu + Terra sorb, Fitofos-K + Terra sorb, Fitofos-Zn-Mn + Terra sorb, e testemunha), sendo cada repetição uma bandeja com 176 mudas incluindo a testemunha, a qual não recebeu aplicação. As aplicações foram realizadas via foliar, iniciando-se sete dias antes da coleta das minicepas no mini jardim clonal até os 120 dias de idade das mudas. Os resultados foram comparados pelo teste de Tukey a 5% de probabilidade. Conclui-se que a aplicação de produtos contendo fosfito e silício não reduziu a severidade da bacteriose causada por Xanthonomas sp. em mudas de Eucalyptus urograndis a nível de viveiro. Não houve efeito significativo dos tratamentos nos padrões de qualidade avaliados. Aos 120 dias de idade foi observado, exceto na testemunha, que os demais tratamentos tiveram uma taxa de sobrevivência das mudas adequada, podendo constatar o efeito positivo dos tratamentos nessa variável que é de grande importância econômica em um viveiro de produção mudas. São necessários estudos mais aprofundados com esses elementos em viveiros, um estudo em ambiente totalmente controlado e com a inoculação de um patógeno especifico seria uma alternativa de estudo para maior compreensão do efeito dos fosfitos e silício na produção de mudas. / This study aimed to verify the effect of the application of phosphite and silicon as compounds of plant health and quality clonal seedlings of Eucalyptus hybrid urophylla x Eucalyptus grandis in a commercial nursery. The study consisted of ten treatments, being the same Zincazot, Fitofós-Cu-K Fitofós, Fitofós-Zn-Mn, Silamol, Amorux, Cu + Fitofós earth-sorb, K + Fitofós-earth sorb, Fitofos- Zn-Mn + Terra Sorb, plus the control treatment. The applications were made via foliar once a week from seven days before planting the ministumps 120 days old seedlings. Each treatment consisted of four trays com176 seedlings, each tray a repeat. The results will be compared with the second evaluation values, which was held to 120 after cutting the ministumps. Still they are obtained the results of quality seedlings (IQD), blight severity.Several studies have shown the effects of mineral nutrition on growth and productivity, with emphasis on the role of nutrients in the plant metabolism. Phosphites have been used on agricultural crops, including forest crops, due to the numerous particular advantages of the product as the relative low cost of the raw material, improving the nutritional status of plants and effects on disease control. Thus, that paper also promoted a study about bacteriosis , that according to the authors is a kind of sickness that has one great in young eucalyptus plants in nursery phase. / CNPq: 130258/2014-8

The class of ligands represented by [CpCo(P(O)(OR)2)3]-, L- , were first synthesized by W. Kläui in 1977. These ligands have been found to coordinate to a variety of low and high oxidation state metals through the use of its three P=O oxygen atoms as donors. The ligands act as mono-anionic six electron donors which make them similar to the more widely known cyclopentadienyl ligands, (C5H5-xRx)-, but have electronic properties like those of fluoride or oxide. Also, it has been found that the coordination chemistry of L- resembles the unsubstituted tris(pryrazolyl)hydroborato six electron ligand, (RB(pz)3)-. All three of these ligands can be modified by changing the substituent R. The Kläui ligand offers a good opportunity to synthesize a chiral derivative. In the process to obtain the chiral version, (cyclopentadienyl)tris(biphenyl-phosphito-P)cobaltate(1-), 18, was synthesized from 2,2'-biphenol. This was characterized through NMR, mass spectroscopy, and XPS. Next, a racemic version, (cyclopentadienyl)tris(biphenylphosphito-P)cobaltate(1-), 17, was synthesized from (±)1,1′-bi-2-naphthol. A one-pot synthesis for the rac-binaphthyl phosphite derivative was developed with an increased yield from the previously published synthesis. The racemic version of the ligand was characterized by NMR and mass spectroscopy. The chiral version has not yet been synthesized, however, by following the developed procedure for the non-chiral version, the ligand could be synthesized from optically active 1,1'-bi-2-naphthol. / Master of Science

Une méthode simple et efficace a été développée pour la préparation de ligands bifonctionnels associant les motifs phosphine ou phosphite d'une part, et carbène Nhétérocyclique(NHC) ou imidazolium d'autre part. Dans un premier temps, une série de ligands diphénylphosphine-carbène chiraux portant un centre stéréogène en a de la phosphinea été développée à partir b-hydroxyesters. Une famille de ligands a ainsi été développée afin d'évaluer l'influence de l'encombrement stérique de différents groupements alkyles en a de la phosphine et de la nature des groupements aromatiques portés sur l'imidazole sur leur activité catalytique. L’étude s’est ensuite étendue à la synthèse de ligands de type dialkylphosphine carbène et phosphite-carbène. Ces différents ligands ont été complexés avec des métaux tels que l’iridium ou le rhodium de manière à en étudier l’activité en hydrogénation asymétrique. / A straightforward method for the preparation of new bidentate ligands containing aphosphine or a phosphite and a carbene function was developed. Different phosphorus-imidazolium compounds were prepared according to this method. First, diphenylphosphine-NHC ligands featuring a stereogenic center a to the phosphine were synthesized from b-hydroxyesters. This strategy was then extended to the preparation of phosphite-imidazoliumand dialkylphosphine-imidazolium compounds. Complexation of these phosphorus-NHCligands with different metals like Ir or Rh was performed in order to study there catalytic properties in asymmetric hydrogenation.

A citricultura brasileira ocupa lugar de destaque no agronegócio nacional, sendo o país o maior produtor de laranja e suco de laranja do mundo. A faia (Fagus sylvatica) é uma das principais espécies das florestas na Europa, sendo usada como ornamental e por possui alto valor econômico devido à produção de madeira. Um dos principais entraves no cultivo dessas espécies é a ocorrência de doenças principalmente as causadas por espécies de Phytophthora que além de causar grandes prejuízos, os métodos de controle são difíceis e onerosos. Existem trabalhos na literatura que apontam os fosfitos como alternativa sustentável, eficaz e economicamente viável para o controle de doenças causadas por oomicetos. Entretanto, o Comitê de Ação a Resistência à Fungicidas (FRAC) classifica os fosfitos, como produtos com ingrediente ativo sem mecanismo de ação definido. Neste contexto, este trabalho teve como objetivo avaliar o produto comercial à base de fosfito de potássio, Phytogard&reg; no controle das doenças causadas por Phytophthora nicotianae em citros e Phytophthora plurivora em faia, bem como avaliar através de análises bioquímicas se esse produto induz resistência em plântulas de citros. Além disso, foram realizados estudos in vitro para avaliar o efeito direto do Phytogard&reg; sobre o desenvolvimento de P. nicotianae e P. plurivora e verificar os possíveis mecanismos de ação desse produto sobre esses patógenos. Foram utilizadas plântulas de citros e faia que foram aspergidas com diferentes concentrações de Phytogard&reg; e, posteriormente, inoculadas com os patógenos. Foram avaliadas a incidência das doenças, o consumo de água e a quantidade de DNA dos patógenos nos tecidos das raízes dos hospedeiros. Ao final do experimento, foram realizadas análises bioquímicas dos tecidos das plântulas de citros. Nos experimentos in vitro, o micélio dos patógenos foi exposto a concentrações crescentes de Phytogard&reg; sendo determinado o crescimento micelial, produção de massa fresca de micélio e de zoósporos. Avaliou-se a perda de eletrólitos, peroxidação de lipídios e a atividade da enzima &beta;-1,3 glucanase do micélio exposto ao produto. Foi avaliada também a morfologia das hifas tratadas ou não com o Phytogard&reg; através da técnica de Microscopia Eletrônica de Varredura (MEV). Os resultados mostraram que o Phytogard&reg;, em todas as concentrações aplicadas controla de maneira preventiva as doenças causadas por P. nicotianae e P. plurivora em citros e faia, respectivamente. Em citros, o produto altera a atividade de algumas proteínas relacionadas à patogênese, mas não é possível concluir que o controle seja mediado por indução de resistência. O Phytogard&reg; inibe o crescimento micelial e a produção de zoósporos de P. nicotianae e P. plurivora. Além disso, o produto modifica a morfologia das hifas, atua na permeabilidade de membrana e na síntese de parede celular do micélio dos patógenos. / The Brazilian citrus production is important to national agribusiness, and the country is the largest orange and orange juice world producer. Beech (Fagus sylvatica) is one of the main forest species in Europe and is used as ornamental and also it has a high economic value due to the production of wood. One of the main problems in the cultivation of these species is the occurrence of diseases, mainly caused by Phytophthora species. Besides causing extensive damage control methods are difficult and costly. There are studies in the literature that show phosphites as a sustainable alternative, effective and economically viable for the control of diseases caused by oomycetes. However, the Fungicide Resistance Action Committee (FRAC), classifies the phosphites as products with the active ingredient with no defined mode of action. In this context, this work aimed to evaluate the commercial product based on potassium phosphite Phytogard&reg; on the control of diseases caused by Phytophthora nicotianae in citrus plants and Phytophthora plurivora in beech plants and evaluate through biochemical assays whether this product induces resistance in citrus seedlings. In addition, in vitro studies were carried out to evaluate the direct effect of Phytogard&reg; on the development of P. nicotianae and P. plurivora and to understand the possible mode of action of the product on these pathogens. Citrus seedlings were sprayed with different concentrations of Phytogard&reg; and then inoculated with the pathogen. We evaluated the diseases incidence, water uptake and the amount of pathogens DNA in the host roots. At the end of the experiment, biochemical assays with citrus seedlings were made. In in vitro experiments, the pathogen mycelium was exposed to increasing concentrations of Phytogard&reg; and mycelial growth, production of fresh mycelium and zoospores by these pathogens were determined. We also evaluated the electrolyte leakage, lipid peroxidation and the &beta;-1,3 glucanase activity in the mycelium exposed to the product. It was also evaluated the hyphae morphology from mycelium treated or not with Phytogard&reg; by using scanning electron microscopy. The results showed that in all concentrations of Phytogard&reg; preventively controled diseases caused by P. nicotianae and P. plurivora in citrus and beech plants, respectively. In citrus, the product changed the activities of some pathogenesis-related proteins, but it is not possible to conclude that the control was mediated by resistance induction. The Phytogard&reg; inhibited mycelial growth and zoospore production by P. nicotianae and P. plurivora. Furthermore, the product modified the hyphae morphology, changed membrane permeability and mycelium cell wall synthesis in the pathogens.

Die vorliegende Arbeit befasst sich mit neuartigen Kupfer(I)- und Ruthenium(II)-komplexen und deren Verwendung als CVD-/ALD-Precursoren. Die Synthese Lewis-Basen-stabilisierter Kupfer(I)-β-Diketonat- bzw. -Carboxylat-Komplexe des Typs [LnMX] (M = Cu(I), X = Acetylacetonat, Iminopentenolat, Carboxylat; L = Phosphan PR3, Phos-phit P(OR)3; R = einbindiger, organischer Rest) standen hierbei im Vordergrund. Verbin-dungen des Typs [(PR3)MX] dienten als Ausgangsverbindungen zur Darstellung einkerni-ger Komplexe mit σ Donorliganden. Durch die Wahl der Lewis-Base sowie des β-Diketonato- bzw. Carboxylato-Fragmentes war es möglich, Einfluss auf die Eigenschaften der erhaltenen Komplexe zu nehmen. Somit waren auch die Untersuchung der thermischen Eigenschaften sowie das Abscheideverhalten der Komplexe während der MOCVD zu ana-lysieren. Thermogravimetrische Untersuchungen bzw. MOCVD-Versuche liessen Rück-schlüsse auf die Eignung der Komplexe des Typs [(PR3)MX] zur Abscheidung elementa-ren Kupfers zu. Des Weiteren wurde die Eignung von Ruthenium-Komplexen des Typs RuX2 (X = substituierte Cyclopentadienyle, 2,4-Dimethylpentadienyl, 4-Methylpent-3-en-2-on-yl) zur Erzeugung von elementaren bzw. oxidierten Rutheniums während MOCVD-Versuchen untersucht. Vorhergehende thermische Untersuchungen an den synthetisierten Komplexen liessen erste Rückschlüsse auf deren Eigenschaften zu. Da der Dampfdruck der für CVD-Zwecke eingesetzten Precursoren besonders interessant ist, wurden diese für die verwendeten Ruthenium-Komplexe bestimmt und sowohl untereinander als auch mit Lite-raturwerten verglichen. Ausgewählte Ruthenium-Komplexe wurden zur Erzeugung metal-lischer oder oxidischer Schichten während MOCVD-Versuchen eingesetzt.