SÍNTESE DE ÁCIDOS CUMARINO-3-CARBOXÍLICOS E SUA APLICAÇÃO NA SÍNTESE TOTAL DA AIAPINA, CUMARINA E UMBELIFERONA

The synthesis of 3-coumarin-carboxylic acids and their application to the total synthesis of the natural products ayapin, coumarin, and umbeliferone in undergraduate organic chemistry experiments is described herein. The synthetic approach consists of a one-pot cyclization between salyciladehydes and Meldrum's acid in water to produce the above mentioned acids, followed by decarboxylation under basic or radical conditions.

Reconstruction tridimensionnelle pour projection sur surfaces arbitraires.

Ce mémoire s'inscrit dans le domaine de la vision par ordinateur. Elle s'intéresse à la calibration de systèmes de caméras stéréoscopiques, à la mise en correspondance caméra-projecteur, à la reconstruction 3D, à l'alignement photométrique de projecteurs, au maillage de nuages de points, ainsi qu'au paramétrage de surfaces. Réalisé dans le cadre du projet LightTwist du laboratoire Vision3D, elle vise à permettre la projection sur grandes surfaces arbitraires à l'aide de plusieurs projecteurs. Ce genre de projection est souvent utilisé en arts technologiques, en théâtre et en projection architecturale. Dans ce mémoire, on procède au calibrage des caméras, suivi d'une reconstruction 3D par morceaux basée sur une méthode active de mise en correspondance, la lumière non structurée. Après un alignement et un maillage automatisés, on dispose d'un modèle 3D complet de la surface de projection. Ce mémoire introduit ensuite une nouvelle approche pour le paramétrage de modèles 3D basée sur le calcul efficace de distances géodésiques sur des maillages. L'usager n'a qu'à délimiter manuellement le contour de la zone de projection sur le modèle. Le paramétrage final est calculé en utilisant les distances obtenues pour chaque point du modèle. Jusqu'à maintenant, les méthodes existante ne permettaient pas de paramétrer des modèles ayant plus d'un million de points.

O projeto politico pedagógico de enfermagem e o sistema único de saúde: a visão de discentes

This research aims to analyze, in the view of students, the pedagogic project of undergraduate nursing course, of UFRN, and its articulation with the SUS, in an attempt to understand the issues that permeate the teaching and learning of nursing. This is a qualitative study that used the focus group technique as a tool to collect empirical data. There were three meetings, where we had the collaboration of 23 graduating students from the eighth period of the semester 2009.1. For the analysis of information, we use a theoretical framework based on curriculum guidelines and basic principles of the SUS, making the analogy of the results with the metaphor of Greek mythology, Ariadne's thread, in dialogue with authors who discuss education as a transformative practice. Thus, the texture of the yarn was built of five thematic fields: joint the pedagogic project with the SUS; the teaching/service and theory/practice relation; interdisciplinarity or transdisciplinarity; didactic/methodological and relational approaches; and co-participation of students in the pedagogic project. According to the discussions, we find many difficulties in the teaching and learning process of undergraduate nursing in UFRN to strengthen the SUS, including: dislocation of educational institutions with services, professionals, managers and community; dichotomy between theory and practice; reality of services as a learning field and working process in health; posture adopted by professionals, teachers and other subjects included in the process of health education; decontextualization and fragmentation of teaching with the practice in health and nursing; excessive use of very illustrative methodologies, but little problem-solving; difficult and precarious situation in the relations between teachers and between teachers/students, regarding the acceptance of differences; absence of participation of students in the evaluation process and conduct of the educational project in progress. In this sense, we understand the need an auto-reflexive act of teaching and conducting collective pedagogical course with a view to achieving the SUS. Thus, it is necessary to support practices motivated by the polyphonic dialogue and the exercise of symbiosis and autopoiesis of subjects/actors jointly responsible for the ongoing process of learning for life.

A aula de História como lugar do ensino, da pesquisa e da extensão

The paper presents a work project developed by the Laboratory of Studies and Research in History Teaching of Unesp/campus Assis (LEPEDIH), which the classroom is understood as a place of construction of historical knowledge through experiences, between students, teachers and future teachers that add teaching, research and extension, in a way that occur the approach between university and public elementary schools in order that participants can relate the study of history with their own life.

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

Paleomegnetic and geochemistry of sediments from the early Aptian Oceanic Anoxic Event

The early Aptian Oceanic Anoxic Event (OAE1a, 120 Ma) represents a geologically brief time interval in the mid-Cretaceous greenhouse world that is characterized by increased organic carbon accumulation in marine sediments, sudden biotic changes, and abrupt carbon-isotope excursions indicative of significant perturbations to global carbon cycling. The brevity of these drastic environmental changes (< 10**6 year) and the typically 10**6 year temporal resolution of the available chronologies, however, represent a critical gap in our knowledge of OAE1a. We have conducted a high-resolution investigation of three widely distributed sections, including the Cismon APTICORE in Italy, Santa Rosa Canyon in northeastern Mexico, and Deep Sea Drilling Project (DSDP) Site 398 off the Iberian margin in the North Atlantic Ocean, which represent a range of depositional environments where condensed and moderately expanded OAE1a intervals are recorded. The objectives of this study are to establish orbital chronologies for these sections and to construct a common, high-resolution timescale for OAE1a. Spectral analyses of the closely-spaced (corresponding to ~5 to 10 kyr) measurements of calcium carbonate content of the APTICORE, magnetic susceptibility (MS) and anhysteretic remanent magnetization (ARM) of the Santa Rosa samples, and MS, ARM and ARM/IRM, where IRM is isothermal remanent magnetization, of Site 398 samples reveal statistically significant cycles. These cycles exhibit periodicity ratios and modulation patterns similar to those of the mid-Cretaceous orbital cycles, suggesting that orbital variations may have modulated depositional processes. Orbital control allows us to estimate the duration of unique, globally identifiable stages of OAE1a. Although OAE1a had a duration of ~1.0 to 1.3 Myr, the initial perturbation represented by the negative carbon-isotope excursion was rapid, lasting for ~27-44 kyr. This estimate could serve as a basis for constraining triggering mechanisms for OAE1a.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.

Geochemistry and mineralogy of selected carbonaceous claystones at DSDP Hole 76-534

Four dominant depositions of carbonaceous claystones are recognized to have occurred during the early Aptian to middle Albian at Site 534. There are correlations of stable isotope ratios with organic carbon content and of clay content with clay mineralogy of the samples. Almost all organic carbon in these sequences has very negative terrestrial isotope ratios, and the clay of that age indicates predominance of aluminous montmorillonite, which is thought to be of terrigenous origin. It is suggested that development of coastal vegetation belts and deltaic outbuilding with consequent outpouring of land-plant detritus and terrigenous elastics into the deep basins probably led to formation of the "black shale" facies.

Barremian-Aptian dinoflagellate cyst assemblages

Quantified organic-walled dinoflagellate cyst (dinocyst) assemblages are presented for two sedimentary successions deposited in neritic environments of the Tethys Ocean during the Barremian and Aptian in an attempt to reconcile established dinocyst biostratigraphic schemes for Tethyan and Austral regions. One section is at Angles, southeast France (the Barremian stratotype section); the other is at Deep Sea Drilling Project Site 263, off northwest Australia. We also construct a carbon isotope record for Site 263 using bulk organic carbon. Both sections contain abundant, well-preserved dinocyst assemblages. These are diverse, with 89 taxa identified at Angles and 103 taxa identified at Site 263. Of these, more than 93% are cosmopolitan. When combined with other work at Angles and Site 263, we found that nine dinocysts have their first occurrence (FO) or last occurrence (LO) at both locations. These dinocyst events are, in alphabetical order: LO of Cassiculosphaeridia magna, FO of Criboperidinium? tenuiceras, LO of Kleithriasphaeridium fasciatum, LO of Muderongia staurota, FO of Odontochitina operculata, LO of Phoberocysta neocomica, FO of Prolixosphaeridium parvispinum, FO of Pseudoceratium retusum var. securigerum, and FO of Tehamadinium sousense. Although these events support a Barremian-Aptian age for both sections, their stratigraphic order is not the same in the sections. The d13Corg record at Site 263 displays a characteristic series of changes that have also been recorded in other carbon isotope curves spanning the Late Barremian-Early Aptian. Such independent dating (along with ammonite zones at Angles) suggests that three of the nine dinocyst events are approximately isochronous at Angles and Site 263: the LO of K. fasciatum in the mid Barremian, the FO of P. retusum var. securigerum and the FO of C.? tenuiceras in the earliest Aptian; the other six dinocyst events are diachronous. Dinocyst assemblages at Site 263 can be loosely placed within existing Australian zonation schemes, providing much-needed calibration. Our data suggest that the Muderongia testudinaria Zone ends in sediments of mid Barremian age, the succeeding Muderongia australis Zone extends into the Early Aptian, and the younger Odontochitina operculata Zone begins in Early Aptian deposits. The boundary between the M. australis and O. operculata zones, and the Ovoidinium cinctum (as Ascodinium) Subzone, positioned at the top of the M. australis Zone when present, could not be recognized incontrovertibly. Interestingly, however, this horizon broadly correlates with the onset and extent of the Selli Event, a time of major biogeochemical change.

Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Nitrogen isotopes of bulk sediments for OAE2 samples

Sediment records of the stable isotopic composition of N (d15N) show light d15N values at several sites in the proto-North Atlantic during Oceanic Anoxic Event 2 (OAE 2) at the Cenomanian-Turonian transition (~94 Ma). The low d15N during the event is generally attributed to an increase in N2-fixation and incomplete uptake of ammonium for phytoplankton growth. A compilation of all reliable data for the proto North-Atlantic during OAE 2 demonstrates that the most pronounced negative shift in d15N from pre-OAE 2 to OAE 2 occurs in the open ocean, but with d15N never lower than -3 ppm. Using a box model of N cycling for the proto-North Atlantic during OAE 2, we show that N2-fixation is a major contributor to the d15N signal, especially in the open ocean. Incomplete uptake of ammonium for phytoplankton growth is important in regions dominated by downwelling, with lateral transport of ammonium acting as a major source. In the southern proto-North Atlantic, where bottom waters were euxinic, the light d15N signature is largely explained by upwelling of ammonium . Our study provides an overview of regional differences in d15N in the proto-North Atlantic and highlights the role of lateral exchange of water and nutrients, in addition to local biogeochemical processes, in determining d15N values of OAE 2 sediments.