主链含六元氮杂环聚酰亚胺的合成及性能

聚酰亚胺是一类综合性能优异的耐热高分子材料，不仅具有很高的热性能，机械性能，和化学稳定性，还具有较低的介电常数和热膨胀系数，使它在航空，航天工业，微电子工业等诸多领域获得了广泛的应用。研究发现芳杂环的引入能为聚酰亚胺带来一定特殊的性能，因而由芳杂环单体合成的聚酰亚胺一直备受关注。近年来由含氮杂环的单体合成的聚酰亚胺及其性能不断被报道，这些聚合物具有很优异的性能。研究表明这些优异的性能与酰亚胺环的对称性，芳香性和杂原子带来的极性有关。吡啶、嘧啶等芳杂环是刚性的芳杂环分子，具有很好的耐热性能及化学稳定性能，而且杂环中的N 原子又可与金属离子配位和质子化。因而，含吡啶(或嘧啶)环聚合物在具有很好的热稳定性及化学稳定性同时，还会具有较好的可加工性。本论文以硝基取代的vinamidinium salts，amidine salts和易烯醇化的羰基化合物为原料，通过在碱性条件下的环化反应得到得含吡啶环(或嘧啶环)的硝基化合物；硝基化合物用Pd/C和水合肼还原得到棒状含氮芳杂环二胺：2,5-二(4-氨基苯基)嘧啶，2-氨基-5-(4-氨基苯基)嘧啶，2-(4-氨基苯基)-5-氨基嘧啶，2,5-二(4-氨基苯基)吡啶，和2-(4-氨基苯基)-5-氨基吡啶。通过1H-NMR、13C-NMR、IR、MS及元素分析确证了含氮芳杂环二胺及其中间产物的结构。这种二胺或加一定量对苯二胺与均苯二酐(PMDA)或联苯二酐(BPDA)通过两步法聚合获得一系列聚酰亚胺，通过红外、动态力学、静态力学、热重分析、广角X-Ray衍射等实验测试了该类聚合物的结构、热性能、机械性能及结晶性能。研究表明，所得聚酰亚胺的分子链有很高的规整性，表现出很好的化学稳定性，优异的热性能和机械性能。当PPD的含量为50%时，由相同二酐单体所得的聚合物具有最好的综合性能，其中杂环中氮原子的极性对维持聚合物的热稳定性和聚合物在高温条件下的机械性能性起着很重要的作用。并将PPD的含量为50%的聚酰胺酸胶液通过干-湿纺，热亚胺化，和高温牵伸获得聚酰亚胺纤维，并研究了亚胺化条件和牵伸条件对聚酰亚胺纤维性能的影响。

芳香型螺双内酯衍生物的合成和性能研究

芳香型螺双内酯是一类含双内酯环和螺碳原子这一特定结构的化合物，它是一类具有面不对称性手性化合物。由于这类化合物具有强的刚性使得它们的熔点非常高，而且含有这类结构的聚合物也同样具有良好的热稳定性。另外，螺双内酯化合物由于具有与酸酐相类似的性质，它的衍生化既容易又多样化，有可能从它衍生得到含氮、含磷、含硫等的衍生物。本文通过有机合成、手性拆分和聚合反应讨论了芳香性螺双内酯在这几方面的性质。1. 以对硝基甲苯和多聚甲醛为原料，探索了两种途径合成了二硝基芳香型螺双内酯，并发现在酸性体系中氧化反应可高收率地直接得到二硝基螺双内酯。2. 探索了两种途径合成了二氨基芳香型螺双内酯。经过一系列的对照试验，优化了还原反应条件，发现在低极性溶剂和使用5% Pd/C催化剂的还原条件下，生成一种稳定的芳香型二羟胺类化合物；而在强极性溶剂中和使用10% Pd/C催化剂的还原条件下，发生还原开环反应。通过对二氨基螺双内酯及其中间产物的结构解析，给出了可能的还原机理。3. 以芳香型螺双内酯的三种衍生物为原料，通过内酰胺化反应，合成了五种芳香型螺双内酯内酰胺化合物和二硝基芳香型螺双内酰胺。发现芳香型螺双内酯化合物易于在一个环上发生内酰胺化反应，生成稳定的螺双内酯内酰胺化合物，而芳香型螺双内酰胺则需要在很高的温度下得到且产率较低、不易分离。4. 对螺双内酯化合物的化学拆分进行了探索，找到了芳香型螺双内酯四酸的拆分体系。5. 通过常温溶液聚合得到了一系列含有芳香螺双内酯结构的聚酰胺和聚酰亚胺，其结构由红外光谱和元素分析得到了验证。同时发现它们具有很高的热稳定性、抗氧化性和溶解性。

Carbon-supported Pd–Ir catalyst as anodic catalyst in direct formic acid fuel cell

It was reported for the first time that the electrocatalytic activity of the Carbon-supported Pd-Ir (Pd-Ir/C) catalyst with the suitable atomic ratio of Pd and Ir for the oxidation of formic acid in the direct formic acid fuel cell (DFAFC) is better than that of the Carbon-supported Pd (Pd/C) catalyst, although Ir has no electrocatalytic activity for the oxidation of formic acid. The potential of the anodic peak of formic acid at the Pd-Ir/C catalyst electrode with the atomic ratio of Pd and Ir = 5:1 is 50 mV more negative than that and the peak current density is 13% higher than that at the Pd/C catalyst electrode.

Highly Active Carbon-supported PdSn Catalysts for Formic Acid Electrooxidation

PdSn/C catalysts with different atomic ratios of Pd to Sn were synthesised by a NaBH4 reduction method. Electrochemical tests show that the alloy catalysts exhibit significantly higher catalytic activity and stability for formic acid electrooxidation (FAEO) than the Pd/C catalyst prepared with the same method. XRD and TEM indicate that a particle-size effect is not the main cause for the high performance. XPS confirms that Pd is modified by Sn through an electronic effect which can decrease the adsorption strength of poisonous intermediates on Pd and thus promote the FAEO greatly.

基于2,5-二(4-氨基苯)嘧啶聚酰亚胺的合成及性能表征

1,5-二氮杂戊二烯盐(vinamidium salts)与4-硝基苯甲脒盐在碱性物质的存在下发生成环反应得含嘧啶环的硝基化合物;硝基化合物用Pd/C和水合肼还原得到棒状含氮芳杂环二胺——2,5-二(4-氨基苯基)嘧啶.通过1H-NMR,13C-NMR,IR,MS及元素分析确证了含氮芳杂环二胺及其中间产物的结构.这种二胺或加一定量对苯二胺与均苯二酐(PMDA)或联苯二酐(BPDA)通过两步法聚合获得一系列聚酰亚胺,通过红外、动态力学、静态力学、热重分析、广角X射线衍射等实验测试了该类聚合物的结构、热性能、机械性能及结晶性能.

H-酸合成新工艺-硝基T-酸催化加氢制取氨基T-酸

利用催化技术对现有H-酸生产工艺中的硝基T-酸加氢制取氨基T-酸进行改进.通过对贵金属Pd/C催化剂的研究,讨论了非贵金属镍催化剂用于催化加氢制取氨基T-酸的可能性.

A comparative study of the synthesis of 3-substituted catechols using an enzymatic and a chemoenzymatic method

A series of cis-dihydrodiol metabolites, available from the bacterial dioxygenase-catalysed oxidation of monosubstituted benzene substrates using Pseudomonas putida UV4, have been converted to the corresponding catechols using both a heterogeneous catalyst (Pd/C) and a naphthalene cis-diol dehydrogenase enzyme present in whole cells of the recombinant strain Escherichia coli DH5 alpha(pUC129: nar B). A comparative study of the merits of both routes to 3-substituted catechols has been carried out and the two methods have been found to be complementary. A similarity in mechanism for catechol formation under both enzymatic and chemoenzymatic conditions, involving regioselective oxidation of the hydroxyl group at C-1, has been found using deuterium labelled toluene cis-dihydrodiols. The potential, of combining a biocatalytic step (dioxygenase-catalysed cis-dihydroxylation) with a chemocatalytic step (Pd/C-catalysed dehydrogenation), into a one-pot route to catechols, from the parent substituted benzene substrates, has been realised.

Fabrication, caractérisation et étude électrochimique de microcapsules conductrices à base de dérivés carbazole aminés pour la conception de biopiles enzymatiques

L’objectif général de cette thèse est de développer une plateforme d’immobilisation d’enzymes efficace pour application en biopile. Grâce à la microencapsulation ainsi qu’au choix judicieux des matériaux polymériques pour la fabrication de la plateforme d’immobilisation, l’efficacité du transfert électronique entre l’enzyme encapsulée et l’électrode serait amélioré. Du même coup, les biopiles employant cette plateforme d’immobilisation d’enzymes pourrait voir leur puissance délivrée être grandement augmentée et atteindre les niveaux nécessaires à l’alimentation d’implants artificiels pouvant remplacer des organes telque le pancréas, les reins, le sphincter urinaire et le coeur. Dans un premier temps, le p-phénylènediamine a été employé comme substrat pour la caractérisation de la laccase encapsulée dans des microcapsules de poly(éthylèneimine). La diffusion de ce substrat à travers les microcapsules a été étudiée sous diverses conditions par l’entremise de son oxidation électrochimique et enzymatique afin d’en évaluer sa réversibilité et sa stabilité. La voltampérométrie cyclique, l’électrode à disque tournante (rotating disk electrode - RDE) et l’électrode à O2 ont été les techniques employées pour cette étude. Par la suite, la famille des poly(aminocarbazoles) et leurs dérivés a été identifée pour remplacer le poly(éthylèneimine) dans la conception de microcapsules. Ces polymères possèdent sur leurs unités de répétition (mono- ou diamino) des amines primaires qui seraient disponibles lors de la polymérisation interfaciale avec un agent réticulant tel qu’un chlorure de diacide. De plus, le 1,8-diaminocarbazole (unité de répétition) possède, une fois polymérisé, les propriétés électrochimiques recherchées pour un transfert d’électrons efficace entre l’enzyme et l’électrode. Il a toutefois été nécessaire de développer une route de synthèse afin d’obtenir le 1,8-diaminocarbazole puisque le protocole de synthèse disponible dans la littérature a été jugé non viable pour être utilisé à grande échelle. De plus, aucun protocole de synthèse pour obtenir du poly(1,8-diaminocarbazole) directement n’a été trouvé. Ainsi, deux isomères de structure (1,6 et 1,8-diaminocarbazole) ont pu être synthétisés en deux étapes. La première étape consistait en une substitution électrophile du 3,6-dibromocarbazole en positions 1,8 et/ou 1,6 par des groupements nitro. Par la suite, une réaction de déhalogénation réductive à été réalisée en utilisant le Et3N et 10% Pd/C comme catalyseur dans le méthanol sous atmosphère d’hydrogène. De plus, lors de la première étape de synthèse, le composé 3,6-dibromo-1-nitro-carbazole a été obtenu; un monomère clé pour la synthèse du copolymère conducteur employé. Finalement, la fabrication de microcapsules conductrices a été réalisée en incorporant le copolymère poly[(9H-octylcarbazol-3,6-diyl)-alt-co-(2-amino-9H-carbazol-3,6-diyl)] au PEI. Ce copolymère a pu être synthétisé en grande quantité pour en permettre son utilisation lors de la fabrication de microcapsules. Son comportement électrochimique s’apparentait à celui du poly(1,8-diaminocarbazole). Ces microcapsules, avec laccase encapsulée, sont suffisamment perméables au PPD pour permettre une activité enzymatique détectable par électrode à O2. Par la suite, la modification de la surface d’une électrode de platine a pu être réalisée en utilisant ces microcapsules pour l’obtention d’une bioélectrode. Ainsi, la validité de cette plateforme d’immobilisation d’enzymes développée, au cours de cette thèse, a été démontrée par le biais de l’augmentation de l’efficacité du transfert électronique entre l’enzyme encapsulée et l’électrode.

Evidences of the cooperative role of the chemokines CCL3, CCL4 and CCL5 and its receptors CCR1+and CCR5+in RANKL+ cell migration throughout experimental periodontitis in mice

Periodontal disease (PD) is characterized by the inflammatory bone resorption in response to the bacterial challenge, in a host response that involves a series of chemokines supposed to control cell influx into periodontal tissues and determine disease outcome. In this study, we investigated the role of chemokines and its receptors in the immunoregulation of experimental PD in mice. Aggregatibacter actinomycetemcomitans-infected C57BI/6 (WT) mice developed an intense inflammatory reaction and severe alveolar bone resorption, associated with a high expression of CCL3 and the migration of CCR5+, CCR1+ and RANKL+ cells to periodontal tissues. However, CCL3KO-infected mice developed a similar disease phenotype than WT strain, characterized by the similar expression of cytokines (TNF-alpha, IFN-gamma and IL-10), osteoclastogenic factors (RANKL and OPG) and MMPs (MMP-1, MMP-2, MMP-3, TIMP-1 and TIMP-3), and similar patterns of CCR1+, CCR5+ and RANKL+ cell migration. The apparent lack of function for CCL3 is possible due the relative redundancy of chemokine system, since chemokines such as CCL4 and CCL5, which share the receptors CCR1 and CCR5 with CCL3, present a similar kinetics of expression than CCL3. Accordingly, CCL4 and CCL5 kinetics of expression after experimental periodontal infection remain unaltered regardless the presence/absence of CCL3. Conversely, the individual absence of CCR1 and CCR5 resulted in a decrease of leukocyte infiltration and alveolar bone loss. When CCR1 and CCR5 were simultaneously inhibited by met-RANTES treatment a significantly more effective attenuation of periodontitis progression was verified, associated with lower values of bone loss and decreased counts of leukocytes in periodontal tissues. Our results suggest that the absence of CCL3 does not affect the development of experimental PD in mice, probably due to the presence of homologous chemokines CCL4 and CCL5 that overcome the absence of this chemokine. In addition, our data demonstrate that the absence of chemokine receptors CCR1+ and CCR5+ attenuate of inflammatory bone resorption. Finally, our data shows data the simultaneous blockade of CCR1 and CCR5 with MetRANTEs presents a more pronounced effect in the arrest of disease progression, demonstrating the cooperative role of such receptors in the inflammatory bone resorption process throughout experimental PD. (C) 2009 Elsevier Inc. All rights reserved.

Utilizacao do limoneno como doador de hidrogenio na reducao catalitica por transferencia de algumas cetonas cataliticas alfa, beta insaturadas

A hidrogenação catalítica por transferência de hidrogênio, utilizando como doador o limoneno e como catalisador 10% Pd/C foi experimentada em cinco cetonas alicíclicas, α,8-insaturadas de seis membros e em uma cetona alifática α, ß,γ ,δ-insaturada. Vários parâmetros de reação foram investigados e tendo como subtrato modeelo a ísoforone. Observou-se 100% de conversão em todas as enonas testadas e aproximadamente 100% de seletividade em cetona saturada nos casos em que o substrato enônico apresentava metilas geminadsa; estabilidae de anel de quatro membros nas condições reacionais e a não seletividade na redução das ligações olefínicas de cetona α, ß,γ ,δ-insaturada. Constatou-se, além de desproporcionação do doador, a ococrrência de um processo competitivo ded desproporcionação do aceptor, o qual foi insignificante no caso de cetonas possuidoas de metilas geminadas, mas perceptível no caso de cetonas que apresentam hidrogênio em cada um dos outros cinco carbonos do anel.

Síntese e análise estrutural de novos ciclopaladatos e síntese de N-heterociclos a partir de ciclopaladatos e alenos

Os compostos de paládio vêm apresentado uma vasta linha de aplicação, tanto como catalisadores como precursores em reações de síntese orgânica. Dentre esses compostos, os ciclopaladatos, que são compostos cíclicos com uma ligação Pd-heteroátomo, permite a formação de novas estruturas cíclicas contendo algum heteroátomo, como nitrogênio, oxigênio ou enxofre. Neste trabalho foram sintetizadas aminas propargílicas capazes de se coordenar a sais de paládio, formando novos ciclopaladatos através da reação de cloropaladação. Esses compostos se encontram na forma de dímeros e podem apresentar-se como diferentes isômeros. Estudos espectroscópicos, tais como RMN de 1H, 13C e raios-X de monocristais foram realizados para a elucidação estrutural desses novos compostos. Além dos isômeros geométricos clássicos (cisóide e transóide) foram observados pela primeira vez a formação de atropoisômeros. Esses ciclopaladatos, contendo nitrogênio ligado ao paládio, foram testados frente a alenos diferentemente substituídos, mostrando que ocorre a inserção do aleno na ligação Pd-C e, seguido da depaladação, ocorre a formação de novos compostos heterocíclicos a seis membros. Alguns ciclopaladatos, quando em solução, podem apresentar certa instabilidade, ocorrendo a decomposição do ciclopaladato com a regeneração do alcino precursor do respectivo ciclopaladato. Assim, estudou-se a reação de decomposição de diferentes ciclopaladatos, chamada de retrocloropaladação, utilizando a técnica de RMN de 1H em diferentes intervalos de tempo.

The dorsal raphe nucleus exerts opposed control on generalized anxiety and panic-related defensive responses in rats

It has been proposed that the ascending dorsal raphe (DR)-serotonergic (5-HT) pathway facilitates conditioned avoidance responses to potential or distal threat, while the DR-periventricular 5-HT pathway inhibits unconditioned flight reactions to proximal danger. Dysfunction on these pathways would be, respectively, related to generalized anxiety (GAD) and panic disorder (PD). To investigate this hypothesis, we microinjected into the rat DR the benzodiazepine inverse receptor agonist FG 7142, the 5-HT1A receptor agonist 8-OH-DPAT or the GABA(A) receptor agonist muscimol. Animals were evaluated in the elevated T-maze (ETM) and light/dark transition test. These models generate defensive responses that have been related to GAD and PD. Experiments were also conducted in the ETM 14 days after the selective lesion of DR serotonergic neurons by 5,7-dihydroxytriptamine (DHT). In all cases, rats were pre-exposed to one of the open arms of the ETM 1 day before testing. The results showed that FG 7142 facilitated inhibitory avoidance, an anxiogenic effect, while impairing one-way escape, an anxiolytic effect. 8-OH-DPAT, muscimol, and 5,7-DHT-induced lesions acted in the opposite direction, impairing inhibitory avoidance while facilitating one-way escape from the open arm. In the light/dark transition, 8-OH-DPAT and muscimol increased the time spent in the lighted compartment, an anxiolytic effect. The data supports the view that distinct DR-5-HT pathways regulate neural mechanisms underlying GAD and PD. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Chemoenzymatic Synthesis of alpha-Hydroxy-beta-methyl-gamma-hydroxy Esters: Role of the Keto-Enol Equilibrium To Control the Stereoselective Hydrogenation in a Key Step

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Depression in patients with Parkinson's disease: Impact on functioning

Depression is a frequently observed neuropsychiatric phenomenon in Parkinson's disease (PD) and it has been lately considered as a manifestation of such disease. The aim of the study was to investigate the relationship between depression and clinical aspects of PD and to assess the impact of the co-occurrence of such condition on the burden imposed by PD. Fifty Outpatients diagnosed with idiopathic PD according to the London Brain Bank criteria were examined. PD was evaluated using Hoehn & Yahr staging (H&Y), United Parkinson's Disease Rating Scale (UPDRS) and Schwab & England (S&E) functional capacity evaluation. A semi-structured clinical interview was used. The diagnosis of PD was made by neurologist experts on movement disorders, and the diagnosis of depression was trade by a psychiatrist, according to the ICD-10 diagnostic criteria. Depressive symptoms were additionally measured using the Montgomery-Asberg Depression Scale. The analysis of quantitative data was performed using descriptive statistics, Univariate linear regression, T-Student Test and ANOVA. Seventeen (34%) patients were diagnosed as clinically depressed and, when compared to the non-depressed ones, presented the following results: H&Y: 3.2 vs. 2.8; UPDRS total: 75.7 vs. 65.3; S&E: 53.5% vs. 65.8% and PD duration: 114.4 months vs. 125.8 months. Depressed patients showed more advanced staging (H&Y), a more severe global clinical condition (UPDRS) and also a greater decrease in their functional capacity (S&E). These data reinforce the hypothesis that depression is associated to poorer functioning in patients with PD. (C) 2008 Elsevier B.V All rights reserved.

Chemical and spectroscopic studies of a new palladium(II) complex with N-acetyl-L-cysteine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)