The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium bis (trifluoromethanesulfonyl) imide [N6,2,2,2][N(Tf)2], 1-butyl-3-methylimidazolium hexafluorosphosphate [C4mim][PF6], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C4mpyrr][N(Tf)2], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][N(Tf)2], N-butyl-N-methyl-pyrrolidinium dicyanamide [C4mpyrr][N(NC)2] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][FAP] on a platinum microelectrode. In [N6,2,2,2][NTf2] and [P14,6,6,6][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion, which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P14,6,6,6][FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N6,2,2,2][NTf2] and [P14,6,6,6][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer is followed by a chemical reaction. © 2009 Elsevier B.V.

Estructura del gasto de consumo de los hogares según finalidad del gasto, por grupos de ingreso

Incluye Bibliografía

Estrus synchronization and fixed time artificial insemination (FTAI) in dairy buffaloes during seasonal anestrus

The aim of this work was to study estrus synchronization and fixed time artificial insemination (FTAI) in dairy buffaloes during season anestrus. One hundred thirty-nine dairy buffaloes in seasonal anestrus were divided in two groups as G1(n=66) and G2(n=73). The protocols for both the groups were the same until day (D)14:D0 administration of 2.0 mg estradiol benzoate and implantation of progesterone device (P4) for 14 days; D14 removal of P4 plus 150 mg of cloprostenol and 400 IU of equine chorionic gonadotropin. On D16, G1 received 10 mg of buserelin and G2 100 mg deslorelin acetate. On D17, both the groups were submitted to FTAI. Ultrasonographic examinations of ovaries were performed on D0, D14, D16 and D17. Results showed that pregnancy rates in G1 and G2 were 20 and 41% (p<0.05) and the ovulation rates were 16.6 and 37%, respectively (p<0.05). The dominant follicle (DF) diameter on D16 was 7.9 mm in G1 and 8.9 mm in G2 (p>0.05). Thirty-five percent of the animals in G1 and 54.1% in G2 showed a diameter DF greater than 8.0 mm on D16 (p>0.05). Thus, it could be concluded that the protocols synchronized the estrus, leading the concentration of the parturitions in the period of low milk production. Deslorelin was more efficient than buserelin due the higher percentage of DF ovulation and higher pregnancy rates.

Determination of in situ speciation of manganese in treated acid mine drainage water by using multiple diffusive gradients in thin films devices

Acid mine drainage (AMD) is a serious environmental problem that creates acidic solution with high Mn concentrations. The speciation of residual Mn from AMD after an active treatment involving the addition of a neutralizing agent can reliably evaluate the treatment efficiency and provide knowledge of the Mn species being inputted into the environment. The aim of this study was to evaluate the in situ lability and speciation of Mn using the diffusive gradients in thin films (DGT) technique with treated drainage water from a uranium mine (TAMD). DGT devices with different binding phases (Chelex-100 and P81 and DE81membranes) were used to perform the in situ speciation of Mn. A comparison of the results from deploying DGT in the laboratory and in situ shows that the speciation of Mn in TAMD should be performed in situ. Linear deployment curves (from in situ experiments) indicate that the DGT device containing the Chelex-100 binding phase can be used to evaluate Mn lability in TAMD. The labile Mn fraction (from in situ measurements) obtained using the device containing the Chelex-100 resin ranged from 63 to 81% of the total Mn concentration and, when compared to the speciation obtained using the CHEAQS software, indicated that this device was capable of uptaking the free Mn2+ and a portion of the MnSO4(aq). The values obtained using the DGT technique were compared to those from on site solid phase extraction, and a good agreement was found between the results. The amount of negative Mn species sampled by DE81 device was insignificant (<1.5%) for all of the sites. Sites containing a relatively small amount of Ca (<40mgL-1) and measured using devices containing the P81 membrane agreed with the concentration predicted by the CHEAQS software for positive Mn species (Mn2+ and Mn(OH)+). Nevertheless, the speciation obtained using the CHEAQS software indicated that the concentrations of positive Mn species were underestimated for sites with relatively high Ca concentrations (>150mgL-1), which take place due to the saturation of binding sites in the P81 membrane. © 2013 Elsevier B.V.

Fronteiras (in)visíveis da cidade capitalista: segregação socioespacial no Conjunto Parque Modelo II/Ananindeua-PA

O presente estudo tem como objeto a análise da produção do espaço no interior da cidade capitalista, ratificado historicamente por meio da lógica de desigualdade social que perversamente estabelece a disparidade existente na distribuição de serviços públicos e habitações, através do acesso desigual à moradia, infraestrutura e serviços coletivos, estabelecendo um quadro tenso e contraditório de segregação socioespacial vivenciado por uma grande massa de trabalhadores. Tendo como objetivo apreender o processo de reprodução social dos trabalhadores residentes no Conjunto Parque Modelo II, bairro Curuçambá, no município de Ananindeua a partir das condições de acesso à moradia, infraestrutura e serviços coletivos que definem o processo de segregação socioespacial naquela área. Neste sentido, para que se alcançasse o objetivo proposto pelo trabalho, inicialmente foi desenvolvida pesquisa bibliográfica que subsidiasse a reconstrução sócio - histórica do espaço urbano no município de Ananindeua e no bairro Curuçambá, e posteriormente foi realizada pesquisa de campo estruturada por meio de formulários aplicados junto a uma amostra de 64 (sessenta e quatro) famílias residentes no Conjunto, buscando-se o levantamento de dados que possibilitasse a posterior interpretação das informações obtidas. Com base nos dados, informações e nas análises realizadas, constatou-se que o Conjunto Parque Modelo II em sua gênese e desenvolvimento acompanha a expansão do núcleo urbano central de Ananindeua, sendo constituído em sua maioria por uma população migrante que busca moradia na área visando melhores condições de vida e sobrevivência, por não possuir condições materiais (renda e trabalho) para se instalar ou se manter no centro ou em áreas próximas, e por isso se reproduzem a partir da convivência cotidiana com a violência, ausência de infraestrutura, serviços e equipamentos urbanos precários e da consequente não satisfação de necessidades básicas que revelam a essência do quadro socioeconômico de segregação socioespacial.

Predicting biological parameters of estuarine benthic communities using models based on environmental data

Este trabalho objetivou predizer parâmetros da estrutura de associações macrobentônicas (composição específica, abundância, riqueza, diversidade e equitatividade) em estuários do Sul do Brasil, utilizando modelos baseados em dados ambientais (características dos sedimentos, salinidade, temperaturas do ar e da água, e profundidade). As amostragens foram realizadas sazonalmente em cinco estuários entre o inverno de 1996 e o verão de 1998. Em cada estuário as amostras foram coletadas em áreas não poluídas, com características semelhantes quanto a presença ou ausência de vegetação, profundidade e distância da desenbocadura. Para a obtenção dos modelos de predição, foram utilizados dois métodos: o primeiro baseado em Análise Discriminante Múltipla (ADM) e o segundo em Regressão Linear Múltipla (RLM). Os modelos baseados em ADM apresentaram resultados melhores do que os baseados em regressão linear. Os melhores resultados usando RLM foram obtidos para diversidade e riqueza. É possível então, concluir que modelos como aqui derivados podem representar ferramentas muito úteis em estudos de monitoramento ambiental em estuários.

Continuous vs. segmented second-dimension system gradients for comprehensive two-dimensional liquid chromatography of sugarcane (Saccharum spp.)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

In situ selective determination of methylmercury in river water by diffusive gradient in thin films technique (DGT) using baker's yeast (Saccharomyces cerevisiae) immobilized in agarose gel as binding phase

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

An ancient founder mutation in PROKR2 impairs human reproduction

Congenital gonadotropin-releasing hormone (GnRH) deficiency manifests as absent or incomplete sexual maturation and infertility. Although the disease exhibits marked locus and allelic heterogeneity, with the causal mutations being both rare and private, one causal mutation in the prokineticin receptor, PROKR2 L173R, appears unusually prevalent among GnRH-deficient patients of diverse geographic and ethnic origins. To track the genetic ancestry of PROKR2 L173R, haplotype mapping was performed in 22 unrelated patients with GnRH deficiency carrying L173R and their 30 first-degree relatives. The mutations age was estimated using a haplotype-decay model. Thirteen subjects were informative and in all of them the mutation was present on the same approximate to 123 kb haplotype whose population frequency is 10. Thus, PROKR2 L173R represents a founder mutation whose age is estimated at approximately 9000 years. Inheritance of PROKR2 L173R-associated GnRH deficiency was complex with highly variable penetrance among carriers, influenced by additional mutations in the other PROKR2 allele (recessive inheritance) or another gene (digenicity). The paradoxical identification of an ancient founder mutation that impairs reproduction has intriguing implications for the inheritance mechanisms of PROKR2 L173R-associated GnRH deficiency and for the relevant processes of evolutionary selection, including potential selective advantages of mutation carriers in genes affecting reproduction.

Charakterisierung von Tumorantigenen des kutanen T-Zell Lymphoms

Immuntherapien stellen basierend auf gut charakterisierten, tumorspezifischen Antigenen ein vielversprechendes Konzept in der Tumor-Therapie dar. Für das kutane T-Zell Lymphom (CTCL) sind bislang nur wenige tumorassoziierte Antigene bekannt. In dieser Arbeit konnten ein mögliches Onkogen (PAR-3ta), ein weiteres, putativ Virus-induziertes Antigen (se57-1), neue Antigene und ihre Splicing-Varianten (se70-2, cTAGE-1/2, cTAGE-5), sowie lymphozytenspezifische Differenzierungsantigene (se20-10-Familie) für das CTCL gefunden werden. Auf Grund des Cancer-Testis spezifischen Expressionsprofils kommen die Antigene cTAGE-1 (46% CTCL-Expression), cTAGE-1B (31%) und cTAGE-5A (44%) für eine CTCL-Immuntherapie in Frage. Einige bekannte, spezifische Tumorantigene konnten auch im CTCL nachgewiesen werden: MAGE-A9 (21%), GAGE 3-7b (46%) und MUC-1 (44%). Die Immunogenität konnte mittels der SEREX-Technologie durch reaktive Antikörper gegen rekombinantes MAGE-A9 in 22% der getesteten CTCL-Seren, gegen GAGE in 16% und gegen cTAGE-5A in 15% bewiesen werden. Die cTAGE-mRNAs bilden eine neue Cancer-Testis Antigenfamilie. Die Multigenfamilie ist durch Retrotransposition eines aktiven Gens (cTAGE-5) entstanden, wobei 7 aktive, transkribierte und 7 nicht transkribierte Pseudogene unterschieden werden müssen. Die aktiven Gene cTAGE-1, cTAGE-1B und cTAGE-5A werden tumorspezifisch aus den Chromosomen 18p11.2 und 14 gespliced. Die Testis-CTCL spezifischen mRNAs können häufig auch in anderen Tumoren gefunden werden. Die Antigene cTAGE-1, cTAGE-5, MAGE-A9 und GAGE 3-7b gehören zu den ersten spezifischen Zielstrukturen des CTCLs, die somit für mögliche Immuntherapien in Betracht kommen.

α-ossidazione asimmetrica organocatalizzata di aldeidi ramificate con dibenzoil perossido

In this thesis, the development of an enantioselective oxidation of α-branched aldehydes using covalent organocatalysis is described. At state of the art, the asymmetric organocatalysis approach, gave often serous difficulties for these kind of substrate respect “classic” aldehydes. We have used a primary cinchona alkaloid derived amine (specially the 9-epi-NH2-CDA) to develop the reaction in combinations with additives. With benzoyl peroxide as oxidant and 2-phenylpropionaldehyde as reference substrate, we have tried to optimize this system but we not found great results about enantiomeric excess.

Cultura "Open" e nuovi modelli normativi per la gestione della conoscenza

L'obiettivo della ricerca è di compiere un'analisi dell'impatto della cosiddetta cultura "open" alla luce dell'attuale condizione del World Wide Web. Si prenderà in considerazione, in particolare, la genesi del movimento a partire dalle basi di cultura hacker e la relativa evoluzione nella filosofia del software libero, con il fine ultimo di identificare il ruolo attuale del modello open source nello scenario esistente. L'introduzione al concetto di Open Access completerà la ricerca anche considerando la recente riaffermazione della conoscenza come bene comune all'interno della Società dell'Informazione

Meta-model for calculating the mean energy demand of automated storage and retrieval systems

Energy efficiency has become an important research topic in intralogistics. Especially in this field the focus is placed on automated storage and retrieval systems (AS/RS) utilizing stacker cranes as these systems are widespread and consume a significant portion of the total energy demand of intralogistical systems. Numerical simulation models were developed to calculate the energy demand rather precisely for discrete single and dual command cycles. Unfortunately these simulation models are not suitable to perform fast calculations to determine a mean energy demand value of a complete storage aisle. For this purpose analytical approaches would be more convenient but until now analytical approaches only deliver results for certain configurations. In particular, for commonly used stacker cranes equipped with an intermediate circuit connection within their drive configuration there is no analytical approach available to calculate the mean energy demand. This article should address this research gap and present a calculation approach which enables planners to quickly calculate the energy demand of these systems.

La Mortola : der Garten des Hrn. Thomas Hanbury

nach Prof. Dr. F. A. Flückiger