Vascular endothelial cell-specific phosphotyrosine phosphatase (VE-PTP) activity is required for blood vessel development

VE-PTP, a receptor-type phosphotyrosine phosphatase, associates with the tyrosine kinase receptor Tie-2 and VE-cadherin and enhances the adhesive function of the latter. Here, VE-PTP was found to be restricted to endothelial cells, with a preference for arterial endothelium. Mutant mice expressing a truncated, secreted form of VE-PTP lacking the cytoplasmic and transmembrane domains and the most membrane-proximal extracellular fibronectin type III repeat, showed severe vascular malformations causing lethality at 10 days of gestation. Although blood vessels were initially formed, the intraembryonic vascular system soon deteriorated. Blood vessels in the yolk sac developed into dramatically enlarged cavities. In explant cultures of mutant allantoides, endothelial cells were found next to vessel structures growing as cell layers. No signs for enhanced endothelial apoptosis or proliferation were observed. Thus, the activity of VE-PTP is not required for the initial formation of blood vessels, yet it is essential for their maintenance and remodeling.

Grain size distribution in surface sediments samples of the continental shelf and slope of southeast Greenland

During "Meteor" Cruise 6/1966 in the northwest Atlantic a systematic survey of the bottom topography of the southeast Greenland continental margin was undertaken. Eighty-seven profiles transverse to the shelf edge at distances of 3-4 nautical miles and two longitudinal profiles parallel to the coast were carried out with the ELAC Narrow Beam Echo-Sounder giving a reliable record of even steep slopes. On the basis of the echo soundings the topography and morphology of the continental shelf and slope are evaluated. A detailed bathymetric chart and a serial profile chart were designed as working material for the morphological research. These maps along with the original echograms are morphometrically evaluated. The analysis of the sea bottom features is the basis of a subsequent morphogenetical interpretation, verified and extended by means of interpretation of magnetic data and sediment analysis (grain size, roundness, lithology). The results of the research are expressed in a geomorphological map. The primary findings can be summarized as follows: 1) The southeast Greenland shelf by its bottom topography can be clearly designated as a glacially formed area. The glacial features of the shelf can be classified into two zones nearly parallel to the coast: glacial erosion forms on the inner shelf and glacial accumulation forms on the outer shelf. The inner shelf is characterized by the rugged and hummocky topography of ice scoured plains with clear west/east slope asymmetry. On the outer shelf three types of glacial accumulation forms can be recognized: ice margin deposits with clearly expressed terminal moraines, glacial till plains and glaciomarine outwash fans. Both zones of the shelf can be subdivided into two levels of relief. The ice scoured plains, with average depths of 240 meters (m), are dissected to a maximum depth of 1060 m (Gyldenloves Trough) by trough valleys, which are the prolongations of the Greenland fjords. The banks of the outer shelf, with an average depth of 180 m, surround glacial basins with a maximum depth of 670 meters. 2) The sediments of the continental shelf can be classified as glacial due to their grain size distribution and the degree of roundness of the gravel particles. The ice margin deposits on the outer shelf can be recognized by their high percentage of gravels. On the inner shelf a rock surface is suggested, intermittently covered by glacial deposits. In the shelf troughs fine-grained sediments occur mixed with gravels. 3) Topography and sediments show that the southeast Greenland shelf was covered by an ice sheet resting on the sea floor during the Pleistocene ice-age. The large end moraines along the shelf edge probably indicate the maximum extent of the Wurm shelf ice resting on the sea floor. The breakthroughs of the end moraines in front of the glacial basins suggest that the shelf ice has floated further seaward over the increasing depths. 4) Petrographically the shelf sediments consist of gneisses, granites and basalts. While gneisses and granites occire on the nearby coast, basalt is not known to exist here. Either this material has been drifted by icebergs from the basalt province to the north or exists on the southeast Greenland shelf itself. The last interpretation is supported bythe high portion of basalt contained in the sediment samples taken and the strong magnetic anomalies probably caused by basaltic intrusions. 5) A magnetic profile allows the recognition of two magnetically differing areas which approximately coincide with the glacial erosion and accumulation zones. The inner shelf shows a strong and variable magnetic field because the glacially eroded basement forms the sea floor. The outer shelf is characterized by a weak and homogenous magnetic field, as the magnetized basement lies at greater depthy, buried by a thick cover of glacial sediments. The strong magnetic anomalies of the inner shelf are probably caused by dike swarms, similar to those observed further to the north in the Kangerdlugssuaq Fjord region. This interpretation is supported by the high basalt content of the sediment samples and the rough topography of the ice scoured plains which correlates in general with the magnetic fluctuations. The dike structures of the basement have been differentially eroded by the shelf ice. 6) The continental slope, extending from the shelf break at 313 m to a depth of 1270 m with an average slope of 11°, is characterized by delta-shaped projections in front of the shelf basins, by marginal plateaus, ridges and hills, by canyons and slumping features. The projections could be identified as glaciomarine sediment fans. This conclusion is supported by the strong decrease of magnetic field intensity. The deep sea hills and ridges with their greater magnetic intensities have to be regarded as basement outcrops projecting through the glaciomarine sediment cover. The upper continental rise, sloping seaward at about 2°, is composed of wide sediment fans and slump material. A marginal depression on the continental rise running parallel to the shelf edge has been identified. In this depression bottom currents capable of erosion have been recorded. South of Cape Farvel the depression extends to the accumulation zone of the "Eirik" sedimentary ridge. 7) By means of a study of the recent marine processes, postglacial modification of the ice-formed relief can be postulated. The retention effect of the fjord troughs and the high velocity of the East Greenland stream prevents the glacial features from being buried by sediments. Bottom currents capable of active erosion have only been found in the marginal depression on the continental rise. In addition, at the time of the lowest glacio-eustatic sea level, the shelf bottom was not situated in the zone of wave erosion. Only on the continental slope and rise bottom currents, sediment slumps and turbidity currents have led to significant recent modifications. Considering these results, the geomorphological development of the southeast Greenland continental terrace can be suggested as follows: 1. initial formation of a "peneplain", 2. fluvial incision, 3. submergence, and finally 4. glacial modification.

(Table 1) Mineralogy of veins in basalts at DSDP Hole 61-462A

Numerous veins are present in basalts recovered from Hole 462A, Leg 61 of the Deep Sea Drilling Project. Three mineral assemblages are recognized and stratigraphically controlled. These assemblages are (1) a zeolite-bearing, quartz-poor assemblage which occurs from Core 44 to the bottom of the hole and contains smectite, clinoptilolite, calcite, pyrite, ± chabazite, ± analcime, ± quartz, ± apophyllite, ± talc (?); (2) a quartz-rich, pyrite-bearing assemblage, found between Cores 19 and 29, which contains smectite, calcite, quartz, and pyrite; and (3) a quartz-rich, celadonite-bearing assemblage which occurs from Cores 14 through 17 and contains smectite, calcite, quartz, celadonite, and Fe oxide. These data are interpreted to represent two episodes of vein mineral formation with an oxidative overprint on the more recent. The first episode followed the outpourings of basaltic lavas onto the sea floor. Zeolite-bearing veins were formed at elevated temperatures under low PCO2 while the thermal gradient was high and before a cover of calcareous sediments had formed. The second mineralization episode followed injection of basalt and microdiabase sills into a thick layer of sediments, and produced all the vein minerals now occurring between Cores 14 and 29. These veins formed at lower temperature and higher PCO2 than zeolite-bearing veins. The presence of pyrite indicates a nonoxidative environment. After the initial formation of these veins, oxygenated seawater diffused through the sedimentary cover and oxidized the pyrite and smectite, forming celadonite and Fe oxides.

Geochemistry of ODP Leg 125 peridotites

Trace element analyses (first-series transition elements, Ti, Rb, Sr, Zr, Y, Nb, and REE) were carried out on whole rocks and minerals from 10 peridotite samples from both Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc using a combination of XRF, ID-MS, ICP-MS, and ion microprobe. The concentrations of incompatible trace elements are generally low, reflecting the highly residual nature of the peridotites and their low clinopyroxene content (<2%). Chondrite-normalized REE patterns show extreme U shapes with (La/Sm)n ratios in the range of 5.03-250.0 and (Sm/Yb)n ratios in the range of 0.05-0.25; several samples show possible small positive Eu anomalies. LREE enrichment is common to both seamounts, although the peridotites from Conical Seamount have higher (La/Ce)n ratios on extended chondrite-normalized plots, in which both REEs and other trace elements are organized according to their incompatibility with respect to a harzburgitic mantle. Comparison with abyssal peridotite patterns suggests that the LREEs, Rb, Nb, Sr, Sm, and Eu are all enriched in the Leg 125 peridotites, but Ti and the HREEs exhibit no obvious enrichment. The peridotites also give positive anomalies for Zr and Sr relative to their neighboring REEs. Covariation diagrams based on clinopyroxene data show that Ti and the HREEs plot on an extension of an abyssal peridotite trend to more residual compositions. However, the LREEs, Rb, Sr, Sm, and Eu are displaced off this trend toward higher values, suggesting that these elements were introduced during an enrichment event. The axis of dispersion on these plots further suggests that enrichment took place during or after melting and thus was not a characteristic of the lithosphere before subduction. Compared with boninites sampled from the Izu-Bonin-Mariana forearc, the peridotites are significantly more enriched in LREEs. Modeling of the melting process indicates that if they represent the most depleted residues of the melting events that generated forearc boninites they must have experienced subsolidus enrichment in these elements, as well as in Rb, Sr, Zr, Nb, Sm, and Eu. The lack of any correlation with the degree of serpentinization suggests that low-temperature fluids were not the prime cause of enrichment. The enrichment in the high-field-strength elements also suggests that at least some of this enrichment may have involved melts rather than aqueous fluids. Moreover, the presence of the hydrous minerals magnesio-hornblende and tremolite and the common resorption of orthopyroxene indicate that this high-temperature peridotite-fluid interaction may have taken place in a water-rich environment in the forearc following the melting event that produced the boninites. The peridotites from Leg 125 may therefore contain a record of an important flux of elements into the mantle wedge during the initial formation of forearc lithosphere. Ophiolitic peridotites with these characteristics have not yet been reported, perhaps because the precise equivalents to the serpentinite seamounts have not been analyzed.

Aprender a enseñar juegos motores con otros : De saber jugar a intervenir como profesor de Educación Física

Durante la formación inicial, los estudiantes del profesorado de Educación Física construyen conocimientos teóricos y prácticos alrededor de prácticas corporales ya conocidas y vivenciadas. Aprenden sobre lo aprendido. Redefinen conocimientos prácticos en un nivel mayor de complejidad y abstracción asignándoles valor educativo que fundamentará su intervención profesional. Cuando le enseñan a proponer 'juegos no juegos' (actividades o deportes que presenta como juegos aunque no todos pueden jugar) el estudiante de Educación Física dispone de elementos teóricos que fundamentan el uso del juego como un recurso pedagógico (ya sea, como contenido de otros ejes, o como estrategia metodológica para la enseñanza de deportes o habilidades motoras). Sin embargo, cuando le enseñan a proponer juegos populares para divertirse, encuentra dificultad para planificar y justificar su futura intervención. Los resultados finales de una investigación cualitativa, presentada como tesis de maestría, muestran que en Educación Física se enseñan múltiples formas de juego motor con otros pero un solo modo de jugarlos: el no lúdico. Se enseña a subordinar el modo de jugar a la forma de los juegos propuestos por el profesor. Se enseña a moverse en el marco de lo permitido por las reglas del juego, a poner el cuerpo al servicio del juego

Aprender a enseñar juegos motores con otros : De saber jugar a intervenir como profesor de Educación Física

Durante la formación inicial, los estudiantes del profesorado de Educación Física construyen conocimientos teóricos y prácticos alrededor de prácticas corporales ya conocidas y vivenciadas. Aprenden sobre lo aprendido. Redefinen conocimientos prácticos en un nivel mayor de complejidad y abstracción asignándoles valor educativo que fundamentará su intervención profesional. Cuando le enseñan a proponer 'juegos no juegos' (actividades o deportes que presenta como juegos aunque no todos pueden jugar) el estudiante de Educación Física dispone de elementos teóricos que fundamentan el uso del juego como un recurso pedagógico (ya sea, como contenido de otros ejes, o como estrategia metodológica para la enseñanza de deportes o habilidades motoras). Sin embargo, cuando le enseñan a proponer juegos populares para divertirse, encuentra dificultad para planificar y justificar su futura intervención. Los resultados finales de una investigación cualitativa, presentada como tesis de maestría, muestran que en Educación Física se enseñan múltiples formas de juego motor con otros pero un solo modo de jugarlos: el no lúdico. Se enseña a subordinar el modo de jugar a la forma de los juegos propuestos por el profesor. Se enseña a moverse en el marco de lo permitido por las reglas del juego, a poner el cuerpo al servicio del juego

Neogene and Quaternary paleoenvironmental history at DSDP Leg 71 Holes

The Neogene and Quaternary sedimentary record of Leg 71 and previously drilled sequences from the Southern Ocean reveal evidence of a major late Miocene change of oceanic and glacial conditions in the southern high latitudes during paleomagnetic Chron 9. The characteristics of late Miocene sedimentation and in particular the study of erosional patterns and ice-rafted debris suggest the following conclusions. 1) In the late Miocene, the Polar Front first migrated to the northern latitudes of the Southern Ocean and surface water temperatures became similar to those of today. 2) Extensive ice shelves or ice tongues were not present along the Antarctic margin until late Chron 9 (about 9.0 Ma). 3) Before Chron 9, West Antarctica was occupied by an archipelago and the West Antarctic Sea. 4) Extensive ice shelves formed in the West Antarctic region, eventually coalescing and thickening to form the grounded West Antarctic ice sheet by Chron 9. 5) The newly formed West Antarctic ice sheet was probably unstable and frequently became an ungrounded ice shelf, thus accounting for the scarcity of late Miocene ice-rafted debris. 6) Extensive erosion or nondeposition of sediment was probably the result of increased Antarctic Bottom Water (AABW) formation in the West Antarctic region during the initial formation of extensive West Antarctic ice shelves and during periods when the West Antarctic ice sheet was ungrounded. 7) In the Southwest Atlantic, AABW velocity waned during the latest Miocene. During the late Gilbert Chron a major and permanent change occurred in the pattern of ice-rafting to the South Atlantic, and after 4.35 Ma the increased IRD accumulation rate and frequency of major episodes of IRD accumulation suggest increased stability of the West Antarctic ice sheet. In addition, radiolarian faunas of Hole 514 record at least eight migrations of the Polar Front to the north of the site during the past 4.07 m.y. An apparent increase in the frequency of Polar Front migrations occurred about 2.7-2.6 Ma, possibly in response to oceanic change induced by fluctuations in glacial conditions of the Northern Hemisphere.

Aprender a enseñar juegos motores con otros : De saber jugar a intervenir como profesor de Educación Física

Durante la formación inicial, los estudiantes del profesorado de Educación Física construyen conocimientos teóricos y prácticos alrededor de prácticas corporales ya conocidas y vivenciadas. Aprenden sobre lo aprendido. Redefinen conocimientos prácticos en un nivel mayor de complejidad y abstracción asignándoles valor educativo que fundamentará su intervención profesional. Cuando le enseñan a proponer 'juegos no juegos' (actividades o deportes que presenta como juegos aunque no todos pueden jugar) el estudiante de Educación Física dispone de elementos teóricos que fundamentan el uso del juego como un recurso pedagógico (ya sea, como contenido de otros ejes, o como estrategia metodológica para la enseñanza de deportes o habilidades motoras). Sin embargo, cuando le enseñan a proponer juegos populares para divertirse, encuentra dificultad para planificar y justificar su futura intervención. Los resultados finales de una investigación cualitativa, presentada como tesis de maestría, muestran que en Educación Física se enseñan múltiples formas de juego motor con otros pero un solo modo de jugarlos: el no lúdico. Se enseña a subordinar el modo de jugar a la forma de los juegos propuestos por el profesor. Se enseña a moverse en el marco de lo permitido por las reglas del juego, a poner el cuerpo al servicio del juego

A POLÍTICA DE FORMAÇÃO DO PROFESSOR DE QUÍMICA

Considerando as inúmeras fragilidades em relação à minha própria formação de professora de Química, considerando também as disposições legais e as orientações curriculares das políticas educacionais atuais que incorporam aportes teóricos fundamentais para que a aprendizagem se concretize e considerando ainda que as transformações nos procedimentos pedagógicos não acompanham o desenvolvimento das ciências da educação, este estudo teve com foco de investigação os seguintes problemas: a) os professores de Química que atuam no Ensino Médio estão devidamente formados para enfrentar as exigências colocadas pelos Parâmetros Curriculares Nacional para o Ensino Médio (PCNEM) e a realidade vivida na escola pública? b) O que o professor faz para que o aluno aprenda Química? c) A política de formação do professor de Química dá conta de formar o químico educador? Para obter os dados para responder a estas questões, recorri a uma pesquisa qualitativa de cunho etnográfico, aplicando questionários a um grupo de 12 professores de Química que atuam no Ensino Médio da rede pública estadual da Grande São Paulo. As questões do questionário foram agrupadas em três categorias: aprendizagem de conceitos, aprendizagem de procedimentos e aprendizagem de valores. No anos de 2001, essas categorias foram utilizadas por García Barros e Martinez Losada em pesquisa com professores da educação básica na Espanha, com ênfase nas duas primeiras, para averiguar que tipo de atividades se realiza habitualmente no ensino de Química e para conhecer a importância que os professores respondentes atribuem aos procedimentos que utilizam no processo de ensino. Os dados coletados, analisados à luz de contribuições dos estudiosos que compõem o corpo teórico deste estudo e das propostas contidas nos PCNEM, evidenciam que o saber fazer do professor, como o definem Carvalho e Perez (2002), é fruto de uma formação inicial precária e da quase inexistência de processos de formação continuada na escola.(AU)

A POLÍTICA DE FORMAÇÃO DO PROFESSOR DE QUÍMICA

Considerando as inúmeras fragilidades em relação à minha própria formação de professora de Química, considerando também as disposições legais e as orientações curriculares das políticas educacionais atuais que incorporam aportes teóricos fundamentais para que a aprendizagem se concretize e considerando ainda que as transformações nos procedimentos pedagógicos não acompanham o desenvolvimento das ciências da educação, este estudo teve com foco de investigação os seguintes problemas: a) os professores de Química que atuam no Ensino Médio estão devidamente formados para enfrentar as exigências colocadas pelos Parâmetros Curriculares Nacional para o Ensino Médio (PCNEM) e a realidade vivida na escola pública? b) O que o professor faz para que o aluno aprenda Química? c) A política de formação do professor de Química dá conta de formar o químico educador? Para obter os dados para responder a estas questões, recorri a uma pesquisa qualitativa de cunho etnográfico, aplicando questionários a um grupo de 12 professores de Química que atuam no Ensino Médio da rede pública estadual da Grande São Paulo. As questões do questionário foram agrupadas em três categorias: aprendizagem de conceitos, aprendizagem de procedimentos e aprendizagem de valores. No anos de 2001, essas categorias foram utilizadas por García Barros e Martinez Losada em pesquisa com professores da educação básica na Espanha, com ênfase nas duas primeiras, para averiguar que tipo de atividades se realiza habitualmente no ensino de Química e para conhecer a importância que os professores respondentes atribuem aos procedimentos que utilizam no processo de ensino. Os dados coletados, analisados à luz de contribuições dos estudiosos que compõem o corpo teórico deste estudo e das propostas contidas nos PCNEM, evidenciam que o saber fazer do professor, como o definem Carvalho e Perez (2002), é fruto de uma formação inicial precária e da quase inexistência de processos de formação continuada na escola.(AU)

Anticoagulant repertoire of the hookworm Ancylostoma caninum.

Hookworms are hematophagous nematodes that infect a wide range of mammalian hosts, including humans. There has been speculation for nearly a century as to the identity of the anticoagulant substances) used by these organisms to subvert host hemostasis. Using molecular cloning, we describe a family of potent small protein (75-84 amino acids) anticoagulants from the hookworm Ancylostoma caninum termed AcAP (A. caninum anticoagulant protein). Two recombinant AcAP members (AcAP5 and AcAP6) directly inhibited the catalytic activity of blood coagulation factor Xa (fXa), while a third form (AcAPc2) predominantly inhibited the catalytic activity of a complex composed of blood coagulation factor VIIa and tissue factor (fVIIa/TF). The inhibition of fVIIa/TF was by a unique mechanism that required the initial formation of a binary complex of the inhibitor with fXa at a site on the enzyme that is distinct from the catalytic center (exo-site). The sequence of AcAPc2 as well as the utilization of an exo-site on fXa distinguishes this inhibitor from the mammalian anticoagulant TFPI (tissue factor pathway inhibitor), which is functionally equivalent with respect to fXa-dependent inhibition of fIIa/TF. The relative sequence positions of the reactive site residues determined for AcAP5 with the homologous regions in AcAP6 and AcAPc2 as well as the pattern of 10 cysteine residues present in each of the inhibitors suggest that the AcAPs are distantly related to the family of small protein serine protease inhibitors found in the nonhematophagous nematode Ascaris lumbricoides var. suum.

Human immunodeficiency virus reverse transcriptase substrate-induced conformational changes and the mechanism of inhibition by nonnucleoside inhibitors.

A combination of transient kinetic and equilibrium titration methods has been used to show that both primer/template and nucleotide binding to human immunodeficiency virus type 1 (HIV-1) reverse transcriptase are two-step processes. In both cases, after initial formation of relatively weakly bound states, isomerization reactions lead to tightly bound states. In the case of deoxynucleotide binding to the reverse transcriptase-primer/template complex, the second step in the interaction is rate-limiting in the overall reaction during processive polymerization. Discrimination against incorrect nucleotides occurs both in the initial weak binding and in the second step but is purely kinetic in the second step (as opposed to thermodynamic in the first step). Nonnucleoside inhibitors have a relatively small effect on nucleotide-binding steps (overall affinity is reduced by a factor of ca. 10), while the affinity of the primer/template duplex is increased by at least a factor of 10. The major effect of nonnucleoside inhibitors is on the chemical step (nucleotide transfer).

Influências do PIBID na representação social de licenciandos em química sobre ser \"professor de química\"

Esta Tese apresenta um estudo sobre a formação inicial de professores de Química em 10 diferentes universidades públicas brasileiras, estabelecidas em 7 diferentes estados e abrange 217 estudantes de licenciatura. Analisou-se a influência do \"Programa Institucional de Bolsas de Iniciação à Docência\" - PIBID - na composição do Núcleo Central (NC) da Representação Social (RS; (MOSCOVICI, 1978) desses Licenciandos sobre o ser \"professor de Química\". Para alocar um termo na zona de centralidade de uma RS é necessário identificar o valor simbólico do termo, refletido em sua saliência, a qual é indicada pela relação entre freqüência e Ordem Média de Evocação e, pelo poder associativo, refletido na conexidade e na categorização temática dos termos. Para a coleta de informações, empregou-se um questionário, com 20 questões, das quais apenas 5 fazem referência específica à tarefa de livre associação de palavras a partir do termo indutor \"professor de Química\", enquanto as demais se referem à caracterização do grupo social. As conclusões deste estudo emergiram da comparação entre o NC da RS de alunos participantes do PIBID (118) com aquele de licenciandos que jamais participaram do Programa (99). Para os alunos participantes dos sub-projetos PIBID-QUÍMICA, os termos do NC da RS investigada são: dedicado, experimentação, responsabilidade. Para o sub-grupo não/PIBID, os termos salientes e com conexidade suficiente para expressar sua centralidade na RS são: dedicado, experimentação, inteligente. Portanto, a zona de centralidade da RS dos dois sub-grupos é diferente, devido a dois termos: responsabilidade e inteligente. O primeiro termo destacado é exclusivo do NC do sub-grupo PIBID, enquanto o último ocorre apenas no NC do sub-grupo não/PIBID. Vale salientar que para o sub-grupo PIBID o termo experimentação apresenta saliência e conexidade expressivos e, para o outro sub-grupo, o termo mais saliente e conexo é dedicado, o que reflete uma diferença qualitativa na organização interna da estrutura das RS, resultado que os caracteriza como diferentes grupos sociais, cada um com uma RS para o ser \"professor de Química\". A presença de termos diferentes na zona de centralidade das RS indica que o processo de formação desenvolvido no âmbito do PIBID expressa a importância da vivência das diferentes práticas pedagógicas junto à Escola Básica durante a formação inicial para a docência em Química, o que não ocorre para o sub-grupo não/PIBID até o momento dos estágios docentes, que demoram muito para acontecer nas Licenciaturas convencionais. No caso do sub-grupo não/PIBID, é forte a presença de termos ligados à idéia de \"vocação\" na docência, expressando aspectos históricos resistentes à mudança no processo de formação de professores.

Study of dopamine reactivity on platinum single crystal electrode surfaces

Dopamine is the biological molecule responsible, among other functions, of the heart beat and blood pressure regulation. Its loss, in the human body, can result in serious diseases such as Parkinson's, schizophrenia or depression. Structurally, this molecule belongs to the group of catecholamines, together with epinephrine (adrenaline) and norepinephrine (noradrenaline). The hydroquinone moiety of the molecule can be easily oxidized to quinone, rendering the electrochemical methods a convenient approach for the development of dopamine biosensors. The reactivity of similar aromatic molecules, such as catechol and hydroquinone, at well-ordered platinum surfaces, has recently been investigated in our group. In this paper, we extend these studies to the structurally related molecule dopamine. The study has been performed in neutral pH, since this is closer to the natural conditions for these molecules in biological media. Cyclic voltammetry and in situ infra-red spectroscopy have been combined to extract information about the behavior of this molecule on well-defined platinum surfaces. Dopamine appears to be electrochemically active and reveals interesting adsorption phenomena at low potentials (0.15–0.25 V vs RHE), sensitive to the single crystal orientation. The adsorption of dopamine on these surfaces is very strong, taking place at much lower potentials than the electron transfer from solution species. Specifically, the voltammetry of Pt(1 1 1) and Pt(1 0 0) in dopamine solutions shows an oxidation peak at potentials close to the onset of hydrogen evolution, which is related to the desorption of hydrogen and the adsorption of dopamine. On the other hand, adsorption on Pt(1 1 0) is irreversible and the surface appears totally blocked. Spectroscopic results indicate that dopamine is adsorbed flat on the surface. At potentials higher than 0.6 V vs RHE the three basal planes show a common redox process. The initial formation of the quinone moiety is followed by a chemical step resulting in the formation of 5,6-dihydroxyindoline quinone as final product. This oxidation process has also been investigated by vibrational spectroscopy.

DAS GESPRÄCH ZWISCHEN HÖLDERLIN, HEGEL UND SCHELLING ÜBER KANTS ANTINOMIEN

«Die Art, wie er den Mechanismus der Natur mit ihrer Zweckmäßigkeit vereiniget, scheint mir eigentlich den ganzen Geist seines Systems zu enthalten»: This quotation, which originated the present essay, is solely extracted from a letter sent by Hölderlin to Hegel, and yet, it condensates three different approaches from the three Tübingen friends to the problem of Kant’s philosophy of religion and to its possible resolution between 1795 and 1796. From this epistolary dialogue emerges a simultaneous study of Kant, originated by the growing dissension towards the orthodox thought of the Stift. The turning point – or the maximum cumulative point – of this discordance happens precisely with the discovery of the «spirit of Kant’s system», as a combined explanation of the religious and philosophical phenomena [«Die Art, wie er den Mechanismus der Natur mit ihrer Zweckmässigkeit vereiniget»]. This, I think, is something which the three friends discover gradually and not independently from the concept of «providence», which Kant himself, according to Hölderlin, had used to «attenuate his antinomies», which Hegel uses in his first religious writings and the initial formation of his own philosophy and which Schelling will later explore in his System of Transcendental Idealism. In a word, providence is consensually the comprehension axis between man, God and nature and, thus, the explanatory link between the antinomical poles which regulate human existence. On the other hand, however – this being the aspect I would like to stress –, this decisive moment for a whole generation, for the history of philosophy itself, means the consummation of a new revolutionary perspective born in Kant, a new vision of the absolute and the divine and, therefore, a new way to write philosophy about philosophy, less philosophical than before, to the extent that the new situation of man and his reflection within the problem ultimately destined them – as is the case in the three young philosophers – to silence and death. The final aim of this essay is, therefore, to know what this «last step of philosophy» is and what dies along with it, what such a step may have meant and what it already foretold in terms of the development of philosophy.