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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Spectroelectrochemical sensing of tris (2,2 bipyridyl) ruthenium (II) dichloride hexahydrate in low ionic strength samples and the spectroelectrochemical characterization of aeruginosin A

Abu, Eme A. 11 September 2012 (has links)
No description available.
2

Filosfera da Mata Atlântica: isolamento e sistemática de cianobactérias, bioprospecção e caracterização da comunidade diazotrófica / Phyllosphere of the Atlantic Forest: isolation and systematic of Cyanobacteria, bioprospection and diazotrophic community characterization

Andreote, Ana Paula Dini 30 January 2014 (has links)
A filosfera da Mata Atlântica é um importante nicho de colonização por micro-organismos, cuja comunidade ainda é pouco conhecida. Algumas bactérias associadas à superfície das folhas possuem habilidade de fixar nitrogênio, mineralizar substratos orgânicos e também suprir as árvores com dióxido de carbono e fatores de crescimento. Este trabalho teve como objetivo gerar informações sobre a comunidade cianobacteriana que coloniza a filosfera de algumas plantas da Mata Atlântica e investigar a comunidade diazotrófica presente nesse habitat. Um total de 40 linhagens de cianobactérias da filosfera de Merostachys neesii (bambu), Euterpe edulis (palmeira Juçara), Guapira opposita e Garcinia gardneriana foram isoladas e cultivadas. Os isolados foram caracterizados por análises morfológicas e filogenia do gene 16S RNAr. Essa abordagem permitiu a identificação de uma linhagem do gênero Nostoc, sete Desmonostoc, seis Leptolyngbya, uma Oculatella, cinco Brasilonema, uma Pleurocapsa e duas Chroococcidiopsis. Dezessete linhagens (uma Microchaetaceae, dez Nostocaceae e seis Pseudanabaenaceae) não puderam ser identificadas ao nível de gênero. Vinte e seis linhagens (24 pertencentes às ordens Nostocales e duas à Pseudanabaenales) foram caracterizadas como diazotróficas pela amplificação, sequenciamento e filogenia do gene nifH. Além disso, caracterizou-se o perfil de fixação biológica de nitrogênio da linhagem Desmonostoc sp. CENA362. Com relação ao potencial biotecnológico dessas linhagens, treze isolados foram identificados como potenciais produtores de ácido indol acético (IAA) de acordo com o teste Salkowski. Diversas linhagens apresentaram genes associados à via biossintética do inibidor de protease microviridina, sendo que três delas codificam para novas variantes. Além disso, dez linhagens foram identificadas como potenciais produtoras aeruginosina, três de cianopeptolina e três de microcistina. A comunidade bacteriana diazotrófica avaliada por pirosequenciamento do gene nifH apresentou um perfil de variação espécie-específica para Proteobacteria e uma correlação positiva entre a riqueza e a fixação biológica de nitrogênio. Neste estudo, cianobactérias que habitam a filosfera da Mata Atlântica foram isoladas estão sendo mantidas em condições de cultivo. Novos táxons foram descobertos e vários gêneros conhecidos foram descritos pela primeira vez neste hábitat, o que contribuiu para o aprimoramento da sistemática de Cyanobacteria. As linhagens em cultivo e as informações geradas sobre os seus compostos metabólitos representam uma valiosa fonte para estudos posteriores. Além disso, informações sobre a comunidade bacteriana diazotrófica da filosfera pode auxiliar no entendimento da dinâmica do nitrogênio, elemento limitante e pouco disponível na Mata Atlântica / The phyllosphere of the Atlantic Forest is an important niche for colonization by microorganisms, whose community is still little known. Some bacteria associated with leaf surfaces may possess the ability to fix nitrogen, mineralize the organic substrates and also supply the trees with carbon dioxide and growth factors. Therefore, this study aimed to generate information about cyanobacterial community that colonize the phyllosphere of some plants of the Atlantic Forest and investigated the diazotrophic community in this habitat. A total of 40 strains of Cyanobacteria from the phyllosphere of Merostachys neesii (bamboo), Euterpe edulis (Juçara palm), Garcinia gardneriana and Guapira opposita was isolated and cultivated. The isolates were characterized by morphological analyses and phylogeny of the 16S rRNA gene. This approach allowed the identification of one strain of the genus Nostoc, seven Desmonostoc, six Leptolyngbya, one Oculatella, five Brasilonema, one Pleurocapsa and two Chroococcidiopsis. Seventeen strains (one Microchaetaceae, ten Nostocaceae and six Pseudanabaenaceae) could not be identified at the genus level. Twenty-six strains (24 belonging to Nostocales and two belonging to Pseudanabaenales) were characterized as diazotrophic by amplification, sequencing and phylogeny of nifH gene. Also, it was characterized the profile of biological nitrogen fixation for the strain Desmonostoc sp. CENA362. Regarding the biotechnological potential of these strains, thirteen strains were identified as potential producers of indole acetic acid (IAA) according to Salkowski test. Several strains presented genes involved in the biosynthetic pathway of the protease inhibitor microviridin, three of them encoding putative novel variants. Moreover, ten strains were identified as potential producers of aeruginosin, three of cyanopeptolin and three of microcystin. The diazotrophic bacterial community evaluated by pyrosequencing of the nifH gene showed a profile of variation plant species-specific for Proteobacteria, and a positive correlation between richness and biological nitrogen fixation. In this study, cyanobacteria that inhabiting Brazilian Atlantic Forest phyllosphere were isolated and are been maintained in culture conditions. New taxa were discovered and several known genera were described for the first time in this habitat, which contributed to improvement of the cyanobacterial systematic. The culturable strains and the information generated about their metabolites compounds represent a valuable source for further studies. In addition, information about the diazotrophic bacterial community inhabiting the phyllosphere may help in understanding the dynamics of nitrogen, a limiting and low available element in Atlantic Forest
3

Filosfera da Mata Atlântica: isolamento e sistemática de cianobactérias, bioprospecção e caracterização da comunidade diazotrófica / Phyllosphere of the Atlantic Forest: isolation and systematic of Cyanobacteria, bioprospection and diazotrophic community characterization

Ana Paula Dini Andreote 30 January 2014 (has links)
A filosfera da Mata Atlântica é um importante nicho de colonização por micro-organismos, cuja comunidade ainda é pouco conhecida. Algumas bactérias associadas à superfície das folhas possuem habilidade de fixar nitrogênio, mineralizar substratos orgânicos e também suprir as árvores com dióxido de carbono e fatores de crescimento. Este trabalho teve como objetivo gerar informações sobre a comunidade cianobacteriana que coloniza a filosfera de algumas plantas da Mata Atlântica e investigar a comunidade diazotrófica presente nesse habitat. Um total de 40 linhagens de cianobactérias da filosfera de Merostachys neesii (bambu), Euterpe edulis (palmeira Juçara), Guapira opposita e Garcinia gardneriana foram isoladas e cultivadas. Os isolados foram caracterizados por análises morfológicas e filogenia do gene 16S RNAr. Essa abordagem permitiu a identificação de uma linhagem do gênero Nostoc, sete Desmonostoc, seis Leptolyngbya, uma Oculatella, cinco Brasilonema, uma Pleurocapsa e duas Chroococcidiopsis. Dezessete linhagens (uma Microchaetaceae, dez Nostocaceae e seis Pseudanabaenaceae) não puderam ser identificadas ao nível de gênero. Vinte e seis linhagens (24 pertencentes às ordens Nostocales e duas à Pseudanabaenales) foram caracterizadas como diazotróficas pela amplificação, sequenciamento e filogenia do gene nifH. Além disso, caracterizou-se o perfil de fixação biológica de nitrogênio da linhagem Desmonostoc sp. CENA362. Com relação ao potencial biotecnológico dessas linhagens, treze isolados foram identificados como potenciais produtores de ácido indol acético (IAA) de acordo com o teste Salkowski. Diversas linhagens apresentaram genes associados à via biossintética do inibidor de protease microviridina, sendo que três delas codificam para novas variantes. Além disso, dez linhagens foram identificadas como potenciais produtoras aeruginosina, três de cianopeptolina e três de microcistina. A comunidade bacteriana diazotrófica avaliada por pirosequenciamento do gene nifH apresentou um perfil de variação espécie-específica para Proteobacteria e uma correlação positiva entre a riqueza e a fixação biológica de nitrogênio. Neste estudo, cianobactérias que habitam a filosfera da Mata Atlântica foram isoladas estão sendo mantidas em condições de cultivo. Novos táxons foram descobertos e vários gêneros conhecidos foram descritos pela primeira vez neste hábitat, o que contribuiu para o aprimoramento da sistemática de Cyanobacteria. As linhagens em cultivo e as informações geradas sobre os seus compostos metabólitos representam uma valiosa fonte para estudos posteriores. Além disso, informações sobre a comunidade bacteriana diazotrófica da filosfera pode auxiliar no entendimento da dinâmica do nitrogênio, elemento limitante e pouco disponível na Mata Atlântica / The phyllosphere of the Atlantic Forest is an important niche for colonization by microorganisms, whose community is still little known. Some bacteria associated with leaf surfaces may possess the ability to fix nitrogen, mineralize the organic substrates and also supply the trees with carbon dioxide and growth factors. Therefore, this study aimed to generate information about cyanobacterial community that colonize the phyllosphere of some plants of the Atlantic Forest and investigated the diazotrophic community in this habitat. A total of 40 strains of Cyanobacteria from the phyllosphere of Merostachys neesii (bamboo), Euterpe edulis (Juçara palm), Garcinia gardneriana and Guapira opposita was isolated and cultivated. The isolates were characterized by morphological analyses and phylogeny of the 16S rRNA gene. This approach allowed the identification of one strain of the genus Nostoc, seven Desmonostoc, six Leptolyngbya, one Oculatella, five Brasilonema, one Pleurocapsa and two Chroococcidiopsis. Seventeen strains (one Microchaetaceae, ten Nostocaceae and six Pseudanabaenaceae) could not be identified at the genus level. Twenty-six strains (24 belonging to Nostocales and two belonging to Pseudanabaenales) were characterized as diazotrophic by amplification, sequencing and phylogeny of nifH gene. Also, it was characterized the profile of biological nitrogen fixation for the strain Desmonostoc sp. CENA362. Regarding the biotechnological potential of these strains, thirteen strains were identified as potential producers of indole acetic acid (IAA) according to Salkowski test. Several strains presented genes involved in the biosynthetic pathway of the protease inhibitor microviridin, three of them encoding putative novel variants. Moreover, ten strains were identified as potential producers of aeruginosin, three of cyanopeptolin and three of microcystin. The diazotrophic bacterial community evaluated by pyrosequencing of the nifH gene showed a profile of variation plant species-specific for Proteobacteria, and a positive correlation between richness and biological nitrogen fixation. In this study, cyanobacteria that inhabiting Brazilian Atlantic Forest phyllosphere were isolated and are been maintained in culture conditions. New taxa were discovered and several known genera were described for the first time in this habitat, which contributed to improvement of the cyanobacterial systematic. The culturable strains and the information generated about their metabolites compounds represent a valuable source for further studies. In addition, information about the diazotrophic bacterial community inhabiting the phyllosphere may help in understanding the dynamics of nitrogen, a limiting and low available element in Atlantic Forest
4

Studies toward the total synthesis of natural and unnatural aeruginosins

Wang, Xiaotian 08 1900 (has links)
Nous avons démontré l’utilité du groupement protecteur tert-butylsulfonyle (N-Bus) pour la chimie des acides aminés et des peptides. Celui-ci est préparé en deux étapes, impliquant la réaction d’une amine avec le chlorure de tert-butylsulfinyle, suivie par l’oxydation par du m-CPBA, pour obtenir les tert-butylsulfonamides correspondants avec d’excellents rendements. Le groupement N-Bus peut être clivé par traitement avec 0.1 N TfOH/DCM/anisole à 0oC en 10h pour régénérer le sel d’ammonium. Une variété d’acides aminés N-Bus protégés ainsi que d’autres aminoacides peuvent alors être utilisés pour préparer divers dipeptides et tripeptides. A l’exception du groupe N-Fmoc, les conditions de déprotection du groupe N-Bus clivent également les groupements N-Boc, N-Cbz et O-Bn. Une déprotection sélective et orthogonale des groupes N-Boc, N-Cbz, N-Fmoc et O-Bn est également possible en présence du groupe protecteur N-Bus. Le nouvel acide aminé non-naturel (3R, 2R) 3–méthyl-D-leucine (β-Me-Leu) et son régioisomère 2-méthyle ont été synthétisés par ouverture d’une N-Ts aziridine en présence d’un excès de LiMe2Cu. Chacun des régioisomères du mélange (1:1,2) a été converti en la méthylleucine correspondante, puis couplé à l’acide D-phényllactique puis au motif 2-carboxyperhydroindole 4-amidinobenzamide en présence de DEPBT. Des élaborations ultérieures ont conduit à des analogues peptidiques non-naturels d’aeruginosines telles que la chlorodysinosine A. Les deux analogues ont ensuite été évalués pour leur activité inhibitrice de la thrombine et la trypsine. La présumée aeruginosine 3-sulfate 205B et son anomère β ont été synthétisés avec succès à partir de 5 sous-unités : la 3-chloroleucine, l’acide D-phényllactique, le D-xylose, le 2-carboxy-6-hydroxyoctahydroindole et l’agmatine. La comparaison des données RMN 1H et 13C reportées avec celles obtenues avec l’aeruginosine synthétique 205B révèle une différence majeure pour la position du groupe présumé 3'-sulfate sur l’unité D-xylopyranosyle. Nous avons alors synthétisés les dérivés méthyl-α-D-xylopyranosides avec un groupement sulfate à chacune des positions hydroxyles, afin de démontrer sans ambiguïté la présence du sulfate en position C-4' par comparaison des données spectroscopiques RMN 1H et 13C. La structure de l’aeruginosine 205B a alors été révisée. Une des étapes-clés de cette synthèse consiste en la formation du glycoside avec le groupe hydroxyle en C-6 orienté en axial sur la sous-unité Choi. Le 2-thiopyridylcarbonate s’est avéré une méthode efficace pour l’activation anomérique. Le traitement par AgOTf et la tétraméthylurée en solution dans un mélange éther-DCM permet d’obtenir l’anomère α désiré, qui peut alors être aisément séparé de l’anomère β par chromatographie / We have demonstrated the usefulness of tert-butylsulfonyl (N-Bus) protecting group in amino acid and peptide chemistry. It is formed in a 2-step procedure involving reaction of an amine with tert-butylsulfinyl chloride, followed by oxidation with m-CPBA to obtain the corresponding tert-butyl- sulfonamides in excellent yields. The N-Bus group can be cleaved to regenerate the corresponding amino salt in 0.1 N TfOH/DCM/anisole at 0 oC for 10 h. A variety of N-Bus protected amino acids and other common amino acids can be used to form dipeptides and tripeptides. With the exception of the N-Fmoc group, the conditions required for the N-Bus group cleavage also cleaved the N-Boc, N-Cbz and O-Bn groups. Selective and orthogonal deprotection of N-Boc, N-Cbz, N-Fmoc and O-Bn groups could be achieved in the presence of the N-Bus protecting group. The new unnatural amino acids (3R, 2R) 3–methyl-D-leucine (β-Me-Leu) and its 2-methyl regioisomer were synthesized by ring opening of an N-Ts aziridine intermediate with excess LiMe2Cu. The 1:1.2 mixture of regioisomers were each converted to the corresponding methyl leucines, then coupled to D-phenyllactic acid, followed by coupling with 2-carboxyperhydroindole 4-amidino-benzamide core in the presence of DEPBT. Further elaboration led to linear peptidic unnatural analogues of known aeruginosins such as chlorodysinosin A. The two analogues were also evaluated in enzymatic assays for their inhibitory activity against thrombin and trypsin. The presumed 3-sulfated aeruginosin 205B and its β–anomer were successfully synthesized from 5 subunits: 3-chloroleucine, D-phenyllactic acid, D-xylose, 2-carboxy-6-hydroxyoctahydroindole, and agmatine. Comparison of 1H and 13C NMR reported data with that of synthetic aeruginosin 205B revealed a disturbing discrepancy with regard to the position of the presumed 3'-sulfate on the D-xylopyranosyl unit. We synthesized methyl α-D-xylopyranosides with sulfates at each of the hydroxyl groups and conclusively demonstrated the the presence of a C-4'-sulfate by comparison of the 1H and 13C NMR spectroscopic data. Thus, the structure of aeruginosin 205B should be revised. One of the key steps in the synthesis is glycoside formation of the axially oriented C-6 hydroxyl group in the Choi subunit. The 2-thiopyridyl carbonate was a suitable method for anomeric activation, followed by treatment with AgOTf and tetramethylurea in ether-DCM solution to give the desired α-anomer, which was easily separable from the β-anomer by column chromatography.
5

Studies toward the total synthesis of natural and unnatural aeruginosins

Wang, Xiaotian 08 1900 (has links)
Nous avons démontré l’utilité du groupement protecteur tert-butylsulfonyle (N-Bus) pour la chimie des acides aminés et des peptides. Celui-ci est préparé en deux étapes, impliquant la réaction d’une amine avec le chlorure de tert-butylsulfinyle, suivie par l’oxydation par du m-CPBA, pour obtenir les tert-butylsulfonamides correspondants avec d’excellents rendements. Le groupement N-Bus peut être clivé par traitement avec 0.1 N TfOH/DCM/anisole à 0oC en 10h pour régénérer le sel d’ammonium. Une variété d’acides aminés N-Bus protégés ainsi que d’autres aminoacides peuvent alors être utilisés pour préparer divers dipeptides et tripeptides. A l’exception du groupe N-Fmoc, les conditions de déprotection du groupe N-Bus clivent également les groupements N-Boc, N-Cbz et O-Bn. Une déprotection sélective et orthogonale des groupes N-Boc, N-Cbz, N-Fmoc et O-Bn est également possible en présence du groupe protecteur N-Bus. Le nouvel acide aminé non-naturel (3R, 2R) 3–méthyl-D-leucine (β-Me-Leu) et son régioisomère 2-méthyle ont été synthétisés par ouverture d’une N-Ts aziridine en présence d’un excès de LiMe2Cu. Chacun des régioisomères du mélange (1:1,2) a été converti en la méthylleucine correspondante, puis couplé à l’acide D-phényllactique puis au motif 2-carboxyperhydroindole 4-amidinobenzamide en présence de DEPBT. Des élaborations ultérieures ont conduit à des analogues peptidiques non-naturels d’aeruginosines telles que la chlorodysinosine A. Les deux analogues ont ensuite été évalués pour leur activité inhibitrice de la thrombine et la trypsine. La présumée aeruginosine 3-sulfate 205B et son anomère β ont été synthétisés avec succès à partir de 5 sous-unités : la 3-chloroleucine, l’acide D-phényllactique, le D-xylose, le 2-carboxy-6-hydroxyoctahydroindole et l’agmatine. La comparaison des données RMN 1H et 13C reportées avec celles obtenues avec l’aeruginosine synthétique 205B révèle une différence majeure pour la position du groupe présumé 3'-sulfate sur l’unité D-xylopyranosyle. Nous avons alors synthétisés les dérivés méthyl-α-D-xylopyranosides avec un groupement sulfate à chacune des positions hydroxyles, afin de démontrer sans ambiguïté la présence du sulfate en position C-4' par comparaison des données spectroscopiques RMN 1H et 13C. La structure de l’aeruginosine 205B a alors été révisée. Une des étapes-clés de cette synthèse consiste en la formation du glycoside avec le groupe hydroxyle en C-6 orienté en axial sur la sous-unité Choi. Le 2-thiopyridylcarbonate s’est avéré une méthode efficace pour l’activation anomérique. Le traitement par AgOTf et la tétraméthylurée en solution dans un mélange éther-DCM permet d’obtenir l’anomère α désiré, qui peut alors être aisément séparé de l’anomère β par chromatographie / We have demonstrated the usefulness of tert-butylsulfonyl (N-Bus) protecting group in amino acid and peptide chemistry. It is formed in a 2-step procedure involving reaction of an amine with tert-butylsulfinyl chloride, followed by oxidation with m-CPBA to obtain the corresponding tert-butyl- sulfonamides in excellent yields. The N-Bus group can be cleaved to regenerate the corresponding amino salt in 0.1 N TfOH/DCM/anisole at 0 oC for 10 h. A variety of N-Bus protected amino acids and other common amino acids can be used to form dipeptides and tripeptides. With the exception of the N-Fmoc group, the conditions required for the N-Bus group cleavage also cleaved the N-Boc, N-Cbz and O-Bn groups. Selective and orthogonal deprotection of N-Boc, N-Cbz, N-Fmoc and O-Bn groups could be achieved in the presence of the N-Bus protecting group. The new unnatural amino acids (3R, 2R) 3–methyl-D-leucine (β-Me-Leu) and its 2-methyl regioisomer were synthesized by ring opening of an N-Ts aziridine intermediate with excess LiMe2Cu. The 1:1.2 mixture of regioisomers were each converted to the corresponding methyl leucines, then coupled to D-phenyllactic acid, followed by coupling with 2-carboxyperhydroindole 4-amidino-benzamide core in the presence of DEPBT. Further elaboration led to linear peptidic unnatural analogues of known aeruginosins such as chlorodysinosin A. The two analogues were also evaluated in enzymatic assays for their inhibitory activity against thrombin and trypsin. The presumed 3-sulfated aeruginosin 205B and its β–anomer were successfully synthesized from 5 subunits: 3-chloroleucine, D-phenyllactic acid, D-xylose, 2-carboxy-6-hydroxyoctahydroindole, and agmatine. Comparison of 1H and 13C NMR reported data with that of synthetic aeruginosin 205B revealed a disturbing discrepancy with regard to the position of the presumed 3'-sulfate on the D-xylopyranosyl unit. We synthesized methyl α-D-xylopyranosides with sulfates at each of the hydroxyl groups and conclusively demonstrated the the presence of a C-4'-sulfate by comparison of the 1H and 13C NMR spectroscopic data. Thus, the structure of aeruginosin 205B should be revised. One of the key steps in the synthesis is glycoside formation of the axially oriented C-6 hydroxyl group in the Choi subunit. The 2-thiopyridyl carbonate was a suitable method for anomeric activation, followed by treatment with AgOTf and tetramethylurea in ether-DCM solution to give the desired α-anomer, which was easily separable from the β-anomer by column chromatography.

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