Aspectos mecanísticos da adição de Michael

The Michael addition reaction has been reported as a conventional nucleophilic process. However, more recently, alternative mechanisms involving electron transfer between acceptor and donnor species have been proposed.

Maritime transportation in the Gulf of Finland in 2007 and in 2015

The Gulf of Finland is said to be one of the densest operated sea areas in the world. It is a shallow and economically vulnerable sea area with dense passenger and cargo traffic of which petroleum transports have a share of over 50 %. The winter conditions add to the risks of maritime traffic in the Gulf of Finland. It is widely believed that the growth of maritime transportation will continue also in the future. The Gulf of Finland is surrounded by three very different national economies with, different maritime transportation structures. Finland is a country of high GDP/per capita with a diversified economic structure. The number of ports is large and the maritime transportation consists of many types of cargoes: raw materials, industrial products, consumer goods, coal and petroleum products, and the Russian transit traffic of e.g. new cars and consumer goods. Russia is a large country with huge growth potential; in recent years, the expansion of petroleum exports has lead to a strong economic growth, which is also apparent in the growth of maritime transports. Russia has been expanding its port activities in the Gulf of Finland and it is officially aiming to transport its own imports and exports through the Russian ports in the future; now they are being transported to great extend through the Finnish, Estonian and other Baltic ports. Russia has five ports in the Gulf of Finland. Estonia has also experienced fast economic growth, but the growth has been slowing down already during the past couples of years. The size of its economy is small compared to Russia, which means the transported tonnes cannot be very massive. However, relatively large amounts of the Russian petroleum exports have been transported through the Estonian ports. The future of the Russian transit traffic in Estonia looks nevertheless uncertain and it remains to be seen how it will develop and if Estonia is able to find replacing cargoes if the Russian transit traffic will come to an end in the Estonian ports. Estonia’s own import and export consists of forestry products, metals or other raw materials and consumer goods. Estonia has many ports on the shores of the Gulf of Finland, but the port of Tallinn dominates the cargo volumes. In 2007, 263 M tonnes of cargoes were transported in the maritime traffic in the Gulf of Finland, of which the share of petroleum products was 56 %. 23 % of the cargoes were loaded or unloaded in the Finnish ports, 60 % in the Russian ports and 17 % in the Estonian ports. The largest ports were Primorsk (74.2 M tonnes) St. Petersburg (59.5 M tonnes), Tallinn (35.9 M tonnes), Sköldvik (19.8 M tonnes), Vysotsk (16.5 M tonnes) and Helsinki (13.4 M) tonnes. Approximately 53 600 ship calls were made in the ports of the Gulf of Finland. The densest traffic was found in the ports of St. Petersburg (14 651 ship calls), Helsinki (11 727 ship calls) and Tallinn (10 614 ship calls) in 2007. The transportation scenarios are usually based on the assumption that the amount of transports follows the development of the economy, although also other factors influence the development of transportation, e.g. government policy, environmental aspects, and social and behavioural trends. The relationship between the development of transportation and the economy is usually analyzed in terms of the development of GDP and trade. When the GDP grows to a certain level, especially the international transports increase because countries of high GDP produce, consume and thus transport more. An effective transportation system is also a precondition for the economic development. In this study, the following factors were taken into consideration when formulating the future scenarios: maritime transportation in the Gulf of Finland 2007, economic development, development of key industries, development of infrastructure and environmental aspects in relation to maritime transportation. The basic starting points for the three alternative scenarios were: • the slow growth scenario: economic recession • the average growth scenario: economy will recover quickly from current instability • the strong growth scenario: the most optimistic views on development will realize According to the slow growth scenario, the total tonnes for the maritime transportation in the Gulf of Finland would be 322.4 M tonnes in 2015, which would mean a growth of 23 % compared to 2007. In the average growth scenario, the total tonnes were estimated to be 431.6 M tonnes – a growth of 64 %, and in the strong growth scenario 507.2 M tonnes – a growth of 93%. These tonnes were further divided into petroleum products and other cargoes by country, into export, import and domestic traffic by country, and between the ports. For petroleum products, the share of crude oil and oil products was estimated and the number of tanker calls in 2015 was calculated for each scenario. However, the future development of maritime transportation in the GoF is dependent on so many societal and economic variables that it is not realistic to predict one exact point estimate value for the cargo tonnes for a certain scenario. Plenty of uncertainty is related both to the degree in which the scenario will come true as well as to the cause-effect relations between the different variables. For these reasons, probability distributions for each scenario were formulated by an expert group. As a result, a range for the total tonnes of each scenario was formulated and they are as follows: the slow growth scenario: 280.8 – 363 M tonnes (expectation value 322.4 M tonnes)

Condutância molecular e biomolecular

The concept of molecular conductance is discussed in terms of the propagation of an electronic interaction, between electron donor and acceptor groups, through the bonds of a molecular structure where these groups are embedded. The electronic interaction propagation is described by a Green's function matrix element, in a donor-bridge-acceptor molecular system reduced to a two-level representation.

Molluscan radiations and landscape evolution in Miocene Amazonia

This PhD study aims to exploit the rich archive provided by the Miocene mollusc fauna of the Pebas Formation and other inland Miocene Amazonian formations to reconstruct landscape evolution and biotic development in lowland Amazonia during the Neogene. Over 160 samples from more than 70 Pebas Formation outcrops mostly collected by the author were processed for this study. Additional samples were collected in Andean areas of Colombia and Venezuela and further material from other northwestern South American basins was studied in museums. Pebas Formation samples and well log data made available by Occidental Peru from three wells in the Marañon Basin in Peru were also investigated. During this study four genera and 74 species from the Pebas Formation have been described and a further 13 species have been introduced in open nomenclature, and several species were reported for the first time. The number of mollusc species attributed to the Pebas fauna has increased from around 50 to 156. The Pebas fauna is characterised as aquatic, endemic and extinct, and is a typical representative of a long-lived lake fauna. Fluvial taxa are not common, (marginal) marine taxa are rare. An additional molluscan fauna from the Miocene Solimões Formation of Brazil, containing 13 fresh water species was also described. The newly documented fauna was used to improve biostratigraphic framework of Miocene Amazonian deposits. Twelve mollusc zones were introduced, the upper eleven of which cover a time interval of approximately seven million years covered previously by only three pollen zones. An age model calculated for the borehole data indicates that the Pebas Formation was deposited between c. 24 and 11 Ma. The areal distribution of the outcropping mollusc zones uncovered a broad dome structure, termed here the Iquitos-Araracuara anteclise in the study area. The structure appears to have influenced river courses and also contributed to edaphic heterogeneity that may have been in part responsible for the current high biodiversity in the study area. The Pebas system was a huge system (> one million km2) dominated by relatively shallow lakes, but also containing swamps and rivers. The system was fed by rivers draining the emergent Andes in the west and lowlands and cratons to the east. The Pebas system was located at sea level and was open to marine settings through a northern portal running through the Llanos Basin and East Venezuela Basin towards the Caribbean. Cyclical baselevel changes possibly related to Mylankhovitch cycles, have been documented in depositional sequences of the Pebas Formation. The composition of the Pebasian mollusc fauna implies that the system was mostly a fresh water system. Such an interpretation is matched by strontium isotope ratios as well as very negative δ18O ratios found in the shells, but is at odds with oligohaline and mesohaline ichnofacies found in the same strata. The mollusc fauna of the Pebas Formation diversified through most of the existence of the lake system. The diversification was mostly the result of in-situ cladogenesis. The success of some of the Pebasian endemic clades is explained by adaptation to fresh water, low oxygen, common unconsolidated lake bottoms (soup grounds) as well as high predation intensity. Maximum diversity was reached at the base of the late Middle to early Late Miocene Grimsdalea pollen zone, some 13 Ma. At the time some 85 species co-occurred, 67 of which are considered as Pebasian endemics. A subsequent drop in species richness coincides with indications of elevated salinities, although a causal relation still needs to be established. Apparently the Pebas fauna went (almost) entirely extinct with the replacement of the lake system into a fluvio-tidal system during the Early Late Miocene, some 11 Ma.

Nanoparticle Labels in Bioaffinity Assays

Nanoparticles offer adjustable and expandable reactive surface area compared to the more traditional solid phase forms utilized in bioaffinity assays due to the high surface to-volume ratio. The versatility of nanoparticles is further improved by the ability to incorporate various molecular complexes such as luminophores into the core. Nanoparticle labels composed of polystyrene, silica, inorganic crystals doped with high number of luminophores, preferably lanthanide(III) complexes, are employed in bioaffinity assays. Other label species such as semiconductor crystals (quantum dots) or colloidal gold clusters are also utilized. The surface derivatization of such particles with biomolecules is crucial for the applicability to bioaffinity assays. The effectiveness of a coating is reliant on the biomolecule and particle surface characteristics and the selected coupling technique. The most critical aspects of the particle labels in bioaffinity assays are their size-dependent features. For polystyrene, silica and inorganic phosphor particles, these include the kinetics, specific activity and colloidal stability. For quantum dots and gold colloids, the spectral properties are also dependent on particle size. This study reports the utilization of europium(III)-chelate-embedded nanoparticle labels in the development of bioaffinity assays. The experimental covers both the heterogeneous and homogeneous assay formats elucidating the wide applicability of the nanoparticles. It was revealed that the employment of europium(III) nanoparticles in heterogeneous assays for viral antigens, adenovirus hexon and hepatitis B surface antigen (HBsAg), resulted in sensitivity improvement of 10-1000 fold compared to the reference methods. This improvement was attributed to the extreme specific activity and enhanced monovalent affinity of the nanoparticles conjugates. The applicability of europium(III)-chelate-doped nanoparticles to homogeneous assay formats were proved in two completely different experimental settings; assays based on immunological recognition or proteolytic activity. It was shown that in addition to small molecule acceptors, particulate acceptors may also be employed due to the high specific activity of the particles promoting proximity-induced reabsorptive energy transfer in addition to non-radiative energy transfer. The principle of proteolytic activity assay relied on a novel dual-step FRET concept, wherein the streptavidin-derivatized europium(III)-chelate-doped nanoparticles were used as donors for peptide substrates modified with biotin and terminal europium emission compliant primary acceptor and a secondary quencher acceptor. The recorded sensitized emission was proportional to the enzyme activity, and the assay response to various inhibitor doses was in agreement with those found in literature showing the feasibility of the technique. Experiments regarding the impact of donor particle size on the extent of direct donor fluorescence and reabsorptive excitation interference in a FRET-based application was conducted with differently sized europium(III)-chelate-doped nanoparticles. It was shown that the size effect was minimal

Propagação da poluição atmosférica por flúor nas águas subterrâneas e solos de regiões próximas às indústrias de fertilizantes (Rio Grande, RS)

Fluoride concentration was determined in rainwater, ground water and soil in the zone of fertilizer industry in the city of Rio Grande. In contaminated rainwater fluorine concentration was registered up to the value of 4,4 mg.L-1. Fluorine concentration in the shallow ground water in general reflects its distribution in the atmosphere, but cannot be used as marker of atmosphere contamination in the urban area due to dissolving influence of residential effluents. The 0,01% HCl extracts from the set of surface soil samples demonstrates fluoride distribution in the zone of influence of industrial emissions, which coincides to the numerical simulation of fluorides dispersion in the air.

Lanthanide Chelates as Donors in Fluorescence Resonance Energy Transfer: Exciting Prospects for Bioaffinity Assay Detection

Fluorescence resonance energy transfer (FRET) is a non-radiative energy transfer from a fluorescent donor molecule to an appropriate acceptor molecule and a commonly used technique to develop homogeneous assays. If the emission spectrum of the donor overlaps with the excitation spectrum of the acceptor, FRET might occur. As a consequence, the emission of the donor is decreased and the emission of the acceptor (if fluorescent) increased. Furthermore, the distance between the donor and the acceptor needs to be short enough, commonly 10-100 Å. Typically, the close proximity between the donor and the acceptor is achieved via bioaffinity interactions e.g. antibody binding antigen. Large variety of donors and acceptors exist. The selection of the donor/acceptor pair should be done not only based on the requirements of FRET but also the performance expectancies and the objectives of the application should be considered. In this study, the exceptional fluorescence properties of the lanthanide chelates were employed to develop two novel homogeneous immunoassays: a non-competitive hapten (estradiol) assay based on a single binder and a dual-parametric total and free PSA assay. In addition, the quenching efficiencies and energy transfer properties of various donor/acceptor pairs were studied. The applied donors were either europium(III) or terbium(III) chelates; whereas several organic dyes (both fluorescent and quenchers) acted as acceptors. First, it was shown that if the interaction between the donor/acceptor complexes is of high quality (e.g. biotin-streptavidin) the fluorescence of the europium(III) chelate could be quenched rather efficiently. Furthermore, the quenching based homogeneous non-competitive assay for estradiol had significantly better sensitivity (~67 times) than a corresponding homogeneous competitive assay using the same assay components. Second, if the acceptors were chosen to emit at the emission minima of the terbium(III) chelate, several acceptor emissions could be measured simultaneously without significant cross-talk from other acceptors. Based on these results, the appropriate acceptors were chosen for the dual-parameter assay. The developed homogeneous dual-parameter assay was able to measure both total and free PSA simultaneously using a simple mix and measure protocol. Correlation of this assay to a heterogeneous single parameter assay was excellent (above 0.99 for both) when spiked human plasma samples were used. However, due to the interference of the sample material, the obtained concentrations were slightly lower with the homogeneous than the heterogeneous assay, especially for the free PSA. To conclude, in this work two novel immunoassay principles were developed, which both are adaptable to other analytes. However, the hapten assay requires a rather good antibody with low dissociation rate and high affinity; whereas the dual-parameter assay principle is applicable whenever two immunometric complexes can form simultaneously, provided that the requirements of FRET are fulfilled.

Functional diversity of macrophyte communities within and between Pyrenean lakes

Submersed vegetation is a common feature in about 70% Pyrene an high mountain (>1500 m a.s.l.) lakes. Isoetids and soft-water elodeids are common elements of this underw ater flora and can form distinct vegetation units (i.e. patches of vegetation dominated by different species) within complex mosaics of vegetation in shallow waters (<7 m). Since is oetids exert a strong influence on sediment biogeochemistry due to high radial oxygen loss, we examined the small scale characteristics of the lake environment (water and sediment) associated to vegetation patches in order to ascertain potential functional differences among them. To do so, we characterised the species composition and biomass of the main vegetation units from 11 lakes, defined plant communities based on biomass data, and then related each community with sediment properties (redox and dissolved nutrient concentration in the pore water) and water nutrient concentration within plant canopy. We also characterised lake water and sediment in areas without vegetation as a reference. A total of twenty-one vegetation units were identified, ranging from one to five per lake. A cluster analysis on biomass species composition suggested seven different macrophyte communities that were named after the most dominant species:Nitella sp.,Potamogeton praelongus, Myriophyllum alterniflorum, Sparganium angustifolium , Isoetes echinospora,Isoetes lacustris and Carex rostrata . Coupling between macrophyte communities and their immediate environment (overlying water and sediment) was manifested mainly as variation in sediment redox conditions and the dominant form of inorganic nitrogen in pore-water. These effects depended on the specific compositi on of the community, and on the allocation between above- and belowground biomass, and could be predicted with a model relating the average and standard deviation of sediment redox potential from 0 down to -20 cm, across macrophyte communities. Differences in pore-water total dissolved phosphorus were related to the trophic state of the lakes. There was no correlation between sediment and water column dissolved nutrients. However, nitrate concentrations tended to be lower in the water overlaying isoetid communities, in apparent contradiction to the patterns of dissolved nitrates in the pore-water. These tendencies were robust even when comparing the water over laying communities within the same lake, thus pointing towards a potential effect of isoetids in reducing dissolved nitrogen in the lakes.

Crassostrea patagonica (d'Orbigny, 1842) shell concentrations from the late Miocene Rio Negro province, NE Patagonia, Argentina

The Río Negro Formation (late Miocene-early Pliocene) mainly consists of continental deposits, but it contains a middle member of marine origin. It represents a transgressive-regressive sequence that can be seen at several outcrops along the N Patagonian coast. The taphonomical approach to the El Espigón marine deposits permits the identification of four main layers containing different kinds of skeletal accumulation, which mainly consist of oyster shells [Crassostrea patagonica (D'Orbigny, 1842)]. These concentrations display three different morphologies (pouches, pavements and bouquets) with a different taphonomic signature. These deposits were formed in shallow marine environments influenced by wave activity that produced valve concentrations of different entities. They contain several shell beds that represent event, composite, hiatal to lag skeletal concentrations. Traces of bioturbation in the sediment (Thalassinoides, Teichichnus) and bioerosion on the shells (Entobia, Gastrochaeonolites, Caulostrepsis), and encrusters (cirripeds, bryozoans), are also abundant in the outcrop and consititue common components of these Miocene materials. Layers 1 and 2 of the sequence were deposited in shoreface/foreshore environments at the beginning of a highstand systems tract, while layers 3 and 4 were deposited at the end, or at the beginning of a forced regression, in foreshore environments. A final erosional episode cut the top of the layer 4, which truncated the abundant bioturbaation developed there.

Ontogenetic dietary changes in male South American fur seals Arctocephalus australis in northern and central Patagonia, Argentina.

This study assessed ontogenetic dietary changes in male South American fur seals Arctocephalus australis in northern and central Patagonia (Argentina) using stable isotope ratios (δ15 N and δ13 C) in vibrissae and bones. Sucking pups were characterised by higher δ15 N values and lower δ13 C values than older specimens. Weaning was associated with a marked drop of δ15 N values, both in bone and vibrissae. Such a drop was inconsistent with the consumption of local prey and may reveal movement to distant foraging grounds or physiological changes associated with either fasting or rapid growth. Stable isotope ratios indicated that juveniles fed more pelagically than subadults and adults, but that there were no major differences between the 2 latter age categories. As subadults and adults are rather similar in body mass and are much larger than juveniles, body mass may play a role in the ontogenetic dietary changes reported. Nevertheless, demersal benthic prey were always scarce in the diet of male fur seals, which relied primarily on Argentine shortfin squid and small pelagic fish throughout life, though adults also consumed large amounts of decapod crustaceans available at shallow depths. Vibrissae did not reveal regular oscillations of δ15 N or δ13 C, except in 1 individual. Thus, male fur seals from northern and central Patagonia do not appear to migrate regularly between isotopically distinct areas, although nomadic displacements cannot be ruled out.

Aplicação de análise de componentes principais para verificação de atribuições de sinais nos espetros de RMN ¹H: o caso dos 3-aril (1,2,4)-oxadiazol-5-carboidrazida benzilidenos

The ¹H NMR data set of a series of 3-aryl (1,2,4)-oxadiazol-5-carbohydrazide benzylidene derivatives synthesized in our group was analyzed using the chemometric technique of principal component analysis (PCA). Using the original ¹H NMR data PCA allowed identifying some misassignments of the proton aromatic chemical shifts. As a consequence of this multivariate analysis, nuclear Overhauser difference experiments were performed to investigate the ambiguity of other assignments of the ortho and meta aromatic hydrogens for the compound with the bromine substituent. The effect of the 1,2,4-oxadiazol group as an electron acceptor, mainly for the hydrogens 12,13, has been highlighted.

Rule-based machine translation between Bulgarian and Macedonian

This paper describes the development of a two-way shallow-transfer rule-based machine translation system between Bulgarian and Macedonian. It gives an account of the resources and the methods used for constructing the system, including the development of monolingual and bilingual dictionaries, syntactic transfer rules and constraint grammars. An evaluation of thesystem's performance was carried out and compared to another commercially available MT system for the two languages. Some future work was suggested.

Zonation patterns of benthic communities in an upwelling area from de western Mediterranean (La Herradura, Alboran Sea)

Species composition and distribution of marine benthic communities from La Herradura (Alboran Sea, western Mediterranean) are described to characterise its rocky and sedimentary bottoms bionomically. Rocky bottoms were studied by means of several underwater transects and soft bottoms with fixed stations along a bathymetric gradient. The study of the floristic and faunistic composition of the rocky benthic communities highlights depth as the main axis of variation. Factorial Correspondence Analysis segregates deep-water communities below 25 m depth (circalittoral communities) from shallower communities (axis I), and communities thriving between 5 and 25 m depth (lower infralittoral communities) from communities thriving close to the surface (shallow infralittoral communities) (axis II). The study of the sedimentary bottoms also suggests that depth, together with physical sedimentary properties, is the main axis of variation in species distribution. Floristic and faunistic records show the particular composition of La Herradura benthic communities, compared to Mediterranean and Atlantic ones. Mixing of Mediterranean and Atlantic waters, together with deep water upwelling episodes typical of this area, probably determine the peculiar composition of the benthic communities

Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis

The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru II(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [Ru II(bpy)3]2+ are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [RuIII(bpy)3] 3+ oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide

Efeitos de substituintes na ligação de hidrogênio do 3-hidroxipropenal

The effect of substituents on the energies and geometries of 3-hydroxypropenal was studied using the B3LYP/6-311++G(d,p) model. The hydrogen bond energies indicate that the strongest donors and the weakest acceptors present the highest and the weakest hydrogen bonds, respectively, indicating the validity of the Madsen RAHB model. Geometric parameters indicate that the intensity of the hydrogen bond is proportional to the resonance, as suggested by the RHAB model. The effect of substituents diverges from the model proposed by Gilli et al. Sometimes the results indicate that the donor or acceptor effect is more important than the point of substitution.