Data collection of Calanus finmarchicus reproduction life history traits in the North Atlantic Ocean

Observations of egg production rates (EPR) for female Calanus finmarchicus were compared from different regions of the North Atlantic. The regions were diverse in size and sampling frequency, ranging from a fixed time series station in the Lower St Lawrence Estuary, off Rimouski, where nearly 200 experiments were carried out between May and December from 1994 to 2006, to a large-scale survey in the Northern Norwegian Sea, where about 50 experiments were carried out between April and June from 2002 to 2004. For this analysis the stations were grouped mostly along geographic lines, with only limited attention being paid to oceanographic features. There is some overlap between regions, however, where stations were sometimes kept together when they were sampled on the same cruise. As well some stations other than off Rimouski were occupied more than once during different years and/or in different seasons.

Nucleophilic addition of Nitrones to Electron deficient acetylenes and related studies

Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

Geochemistry and mineralogy of a silica chimney from an inactive seafloor hydrothermal field (East Pacific Rise, 18°S)

An inactive vent field comprised of dead chimneys was discovered on the ultrafast East Pacific Rise (EPR) at 18°S during the research campaign NAUDUR with the R/V Le Nadir in December 1993. One of these chimneys was sampled, studied and found to be largely composed of silica-mineralized bacterial-like filaments. The filaments are inferred to be the result of microbial activity leading to silica (± Fe-oxyhydroxide) precipitation. The chimney grew from the most external layer (precipitated 226 ± 4 yr. B.P.) towards the central chimney conduit. Hydrothermal activity ceased 154 ± 13 yr. B.P. and the chimney conduit was completely sealed. Mixing between an end-member hydrothermal fluid and seawater explains the Sr–Nd isotopic composition of the chimney. Seawater was the major source of Sr to the chimney, whereas the dominant Nd source was the local mid-ocean ridge basalt (MORB) leached by the hydrothermal fluids. The mixing scenarios point to a dynamic hydrothermal system with fluctuating fluid compositions. The proportion of seawater within the venting fluid responsible for the precipitation of the silica chimney layers varied between 94 and 85%. Pb-isotope data indicates that all of the Pb in the chimney was derived from the underlying MORB. The precipitation temperatures of the chimney layers varied between 55 and 71 °C, and were a function of the seawater/end-member hydrothermal fluid mixing ratio. δ30Si correlates with the temperature of precipitation implying that temperature is one of the major controls of the Si-isotope composition of the chimney. Concentrations of elements across the chimney wall were a function of this mixing ratio and the composition of the end-member hydrothermal fluid. The inward growth of the chimney wall and accompanying decrease in wall permeability resulted in an inward decrease in the seawater/hydrothermal fluid mixing ratio, which in turn exerted a control on the concentrations of the elements supplied mainly by the hydrothermal fluids. The silica chimney is significantly enriched in U, likely a result of bacterial concentration of U from the seawater-dominated vent fluid. The chimney is poor in rare earth elements (REE). It inherited its REE distribution patterns from the parent end-member hydrothermal fluids. The dilution of the hydrothermal fluid with over 85% seawater could not obliterate the particular REE features (positive Eu anomaly) of the hydrothermal fluids.

Applications of functional nucleic acids in imaging, sensing and drug delivery and investigations of DNAzyme-metal interactions

Functional nucleic acids (FNA), including nucleic acids catalysts (ribozymes and DNAzymes) and ligands (aptamers), have been discovered in nature or isolated in a laboratory through a process called in vitro selection. They are nucleic acids with functions similar to protein enzymes or antibodies. They have been developed into sensors with high sensitivity and selectivity; it is realized by converting the reaction catalyzed by a DNAzyme/ribozyme or the binding event of an aptamer to a fluorescent, colorimetric or electrochemical signal. While a number of studies have been reported for in vitro sensing using DNAzymes or aptamers, there are few reports on in vivo sensing or imaging. MRI is a non-invasive imaging technique; smart MRI contrast agents were synthesized for molecular imaging purposes. However, their rational design remains a challenge due to the difficulty to predict molecular interactions. Chapter 2 focuses on rational design of smart T1-weighted MRI contrast agents with high specificity based on DNAzymes and aptamers. It was realized by changing the molecular weight of the gadolinium conjugated DNA strand with the analytes, which lead to analyte-specific water proton relaxation responses and contrast changes on an MRI image. The designs are general; the high selectivity of FNA was retained. Most FNA-based fluorescent sensors require covalent labeling of fluorophore/quencher to FNAs, which incurrs extra expenses and could interfere the function of FNAs. Chapter 3 describes a new sensor design avoiding the covalent labeling of fluorophore and quencher. The fluorescence of malachite green (MG) was regulated by the presence of adenosine. Conjugate of aptamers of MG and adenosine and a bridge strand were annealed in a solution containing MG. The MG aptamer did not bind MG because of its hybridization to the bridge strand, resulting in low fluorescence signal of MG. The hybridization was weakened in the presence of adenosine, leading to the binding of MG to its aptamer and a fluorescence increase. The sensor has comparable detection limit (20 micromolar) and specificity to its labeled derivatives. Enzymatic activity of most DNAzymes requires metal cations. The research on the metal-DNAzyme interaction is of interest and challenge to scientists because of the lack of structural information. Chapters 4 presents the research on the characterization of the interaction between a Cu2+-dependent DNAzyme and Cu2+. Electron paramagnetic resonance (EPR) and UV-Vis spectroscopy were used to probe the binding of Cu2+ to the DNAzyme; circular dichroism was used to probe the conformational change of the DNAzyme induced by Cu2+. It was proposed that the conformational change by the Cu2+ binding is important for the activity of the DNAzyme. Chapter 5 reports the dependence of the activity of 8-17 DNAzyme on the presence of both Pb2+ and other metal cations including Zn2+, Cd2+ and Mg2+. It was discovered that presence of those metal cations can be cooperative or inhibitive to 8-17 activity. It is hypothesized that the 8-17 DNAzyme had multiple binding sites for metal cations based on the results. Cisplatin is effective killing tumor cells, but with significant side effects, which can be minimized by its targeted delivery. Chapter 6 focuses on the effort to functionalize liposomes encapsulating cisplatin by an aptamer that selectively bind nucleolin, an overexpressed protein by breast cancer cells. The study proved the selective cytotoxicity to breast cancer cells of the aptamer-functionalized liposome.

Estudo da influência da morfologia de nanopartículas de sílica mesoporosa na liberação do anticancerígeno indol-3-carbinol

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ceilândia, Programa de Pós-graduação em Ciências e Tecnologias em Saúde, 2015.

Superparamagnetic Liposomes for MRI Monitoring and External Magnetic Field-Induced Selective Targeting of Malignant Brain Tumors

International audience

Satisfying the Einstein-Podolsky-Rosen criterion with massive particles

In 1935, Einstein, Podolsky and Rosen (EPR) questioned the completeness of quantum mechanics by devising a quantum state of two massive particles with maximally correlated space and momentum coordinates. The EPR criterion qualifies such continuous-variable entangled states, where a measurement of one subsystem seemingly allows for a prediction of the second subsystem beyond the Heisenberg uncertainty relation. Up to now, continuous-variable EPR correlations have only been created with photons, while the demonstration of such strongly correlated states with massive particles is still outstanding. Here we report on the creation of an EPR-correlated two-mode squeezed state in an ultracold atomic ensemble. The state shows an EPR entanglement parameter of 0.18(3), which is 2.4 s.d. below the threshold 1/4 of the EPR criterion. We also present a full tomographic reconstruction of the underlying many-particle quantum state. The state presents a resource for tests of quantum nonlocality and a wide variety of applications in the field of continuous-variable quantum information and metrology.

Implementation of continuous-variable quantum key distribution with composable and one-sided-device-independent security against coherent attacks

Secret communication over public channels is one of the central pillars of a modern information society. Using quantum key distribution this is achieved without relying on the hardness of mathematical problems, which might be compromised by improved algorithms or by future quantum computers. State-of-the-art quantum key distribution requires composable security against coherent attacks for a finite number of distributed quantum states as well as robustness against implementation side channels. Here we present an implementation of continuous-variable quantum key distribution satisfying these requirements. Our implementation is based on the distribution of continuous-variable Einstein–Podolsky–Rosen entangled light. It is one-sided device independent, which means the security of the generated key is independent of any memoryfree attacks on the remote detector. Since continuous-variable encoding is compatible with conventional optical communication technology, our work is a step towards practical implementations of quantum key distribution with state-of-the-art security based solely on telecom components.

Seamount abundances and abyssal hill morphology on the eastern flank of the East Pacific Rise at 14 degrees S

Bathymetric data from a Hydrosweep multibeam sonar survey of a 720 km long tectonic corridor on the east flank of the southern EPR at 14 degrees 14'S covered about 25,000 km(2) of zero-age to 8.5 m.y. old crust (magnetic anomaly 4A). In this corridor we document a strong correlation of robust along flowline changes in abyssal hill morphology and seamount size distribution with spreading rate changes deduced from our magnetic data. Indeed, we find that both rms height of abyssal hills and abundance and height of seamounts increase significantly as spreading rate changes from similar to 75 mm/yr to over 85 mm/yr (half rate). Moreover, we identified 46 seamounts taller than 100 m. Previous studies on the southern EPR reported a larger density of seamounts, organized primarily in chains. Our investigation, however, revealed seamounts not associated with major chains, leading us to the conclusion that different forms of off-axis volcanism occur along the spreading center.

The Southeast Indian Ridge between 88°E and 118°E: Gravity anomalies and crustal accretion at intermediate spreading rates

Although slow spreading ridges characterized by a deep axial valley and fast spreading ridges characterized by an axial bathymetric high have been extensively studied, the transition between these two modes of axial morphology is not well understood. We conducted a geophysical-survey of the intermediate spreading rate Southeast Indian Ridge between 88 degrees E and 118 degrees E, a 2300-km-long section of the ridge located between the Amsterdam hot spot and the Australian-Antarctic Discordance where satellite gravity data suggest that the Southeast Indian Ridge (SEIR) undergoes a change from an axial high in the west to an axial valley in the east. A basic change in axial morphology is found near 103 degrees 30'E in the shipboard data; the axis to the west is marked by an axial high, while a valley is found to the east. Although a well-developed axial high, characteristic of the East Pacific Rise (EPR), is occasionally present, the more common observation is a rifted high that is lower and pervasively faulted, sometimes with significant (> 50 m throw) faults within a kilometer of the axis. A shallow axial valley (< 700 m deep) is observed from 104 degrees E to 114 degrees E with a sudden change to a deep (>1200 m deep) valley across a transform at 114 degrees E. The changes in axial morphology along the SEIR are accompanied by a 500 m increase in near-axis ridge flank depth from 2800 m near 88 degrees E to 3300 m near 114 degrees E and by a 50 mGal increase in the regional level of mantle Bouguer gravity anomalies over the same distance, The regional changes in depth and mantle Bouguer anomaly (MBA) gravity can be both explained by a 1.7-2.4 km change in crustal thickness or by a mantle temperature change of 50 degrees C-90 degrees C. In reality, melt supply (crustal thickness) and mantle temperature are linked, so that changes in both may occur simultaneously and these estimates serve as upper bounds. The along-axis MBA gradient is not uniform. Pronounced steps in the regional level of the MBA gravity occur at 103 degrees 30'E-104 degrees E and at 114 degrees E-116 degrees E and correspond to the changes in the nature of the axial morphology and in the amplitude of abyssal hill morphology suggesting that the different forms of morphology do not grade into each other but rather represent distinctly different forms of axial (s)tructure and tectonics with a sharp transition between them. The change from an axial high to an axial valley requires a threshold effect in which the strength of the lithosphere changes quickly. The presence or absence of a quasi-steady state magma chamber may provide such a mechanism. The different forms of axial morphology are also associated with different intrasegment MBA gravity patterns. Segments with an axial high have an MBA low located at a depth minimum near the center of the segment, At EPR-like segments, the MBA low is about 10 mGal with along-axis gradients of 0.15-0.25 mGal/km, similar to those observed at the EPR, Rifted highs have a shallower low and lower gradients suggesting an attenuated composite magma chamber and a reduced and perhaps episodic melt supply. Segments with a shallow axial valley have very flat along-axis MBA profiles with little correspondence between axial depth and axial MBA gravity.

Host-guest chemistry of solid coordination frameworks (SCFs) based on Copper(II)-Pyridine Ligands

283 p.

Reduction capability of soil humic substances from the Rio Negro basin, Brazil, towards Hg(II) studied by a multimethod approach and principal component analysis (PCA)

This paper characterizes humic substances (HS) extracted from soil samples collected in the Rio Negro basin in the state of Amazonas, Brazil, particularly investigating their reduction capabilities towards Hg(II) in order to elucidate potential mercury cycling/volatilization in this environment. For this reason, a multimethod approach was used, consisting of both instrumental methods (elemental analysis, EPR, solid-state NMR, FIA combined with cold-vapor AAS of Hg(0)) and statistical methods such as principal component analysis (PCA) and a central composite factorial planning method. The HS under study were divided into groups, complexing and reducing ones, owing to different distribution of their functionalities. The main functionalities (cor)related with reduction of Hg(II) were phenolic, carboxylic and amide groups, while the groups related with complexation of Hg(II) were ethers, hydroxyls, aldehydes and ketones. The HS extracted from floodable regions of the Rio Negro basin presented a greater capacity to retain (to complex, to adsorb physically and/or chemically) Hg(II), while nonfloodable regions showed a greater capacity to reduce Hg(II), indicating that HS extracted from different types of regions contribute in different ways to the biogeochemical mercury cycle in the basin of the mid-Rio Negro, AM, Brazil. (c) 2007 Published by Elsevier B.V.

Efeitos do treinamento resistido com máquinas pneumáticas e resistência elástica progressiva na força, capacidade funcional e equilíbrio em mulheres idosas : um ensaio clínico randomizado

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Educação Física, Programa de Pós-Graduação Strictu-Sensu em Educação Física, 2015.