Dynamic aggregation of the mid-sized gadolinium complex {Ph-4[Gd(DTTA)(H2O)(2)](-)(3)}

A compound binding three Gd3+ ions, {Ph-4Gd(DTTA)(H2O)(2) (3)} (where H(5)DTTA is diethylenetriaminetetraacetic acid), has been synthesized around a hydrophobic center made up of four phenyl rings. In aqueous solution the molecules start to self-aggregate at concentrations well below 1 mM as shown by the increase of rotational correlation times and by the decrease of the translational self-diffusion constant. NMR spectra recorded in aqueous solution of the diamagnetic analogue {Ph-4Y(DTTA)(H2O)(2) (3)} show that the aggregation is dynamic and due to intermolecular pi-stacking interactions between the hydrophobic aromatic centers. From estimations of effective radii, it can be concluded that the aggregates are composed of two to three monomers. The paramagnetic {Ph-4Gd(DTTA)(H2O)(2) (3)} exhibits concentration-dependent H-1 NMR relaxivities with high values of approximately 50 mM(-1) s(-1) (30 MHz, 25 A degrees C) at gadolinium concentrations above 20 mM. A combined analysis of H-1 NMR dispersion profiles measured at different concentrations of the compound and O-17 NMR data measured at various temperatures was performed using different theoretical approaches. The fitted parameters showed that the increase in relaxivity with increasing concentration of the compound is due to slower global rotational motion and an increase of the Lipari-Szabo order parameter S-2.

Modeling study of the interannual variability in global tropospheric hydroxyl radical and methane concentrations over the last two decades

Jérôme Drevet

Methane (CH4) is a major greenhouse gas whose global warming potential is 23 times more important than carbon dioxide (CO2). CH4 concentrations have steadily increased since the beginning of the industrial era, reaching an unprecedent level (almost 1800 ppb at present times). CH4 is currently considered as a one of the major driver of the climate change and its warming potential has leaded the Kyoto protocol to plan a significative reduction of its emissions. The objective of this thesis is to examine the factors that contribute to the CH4 global budget as well as its year-to-year variations. To that purpose, we have implemented a methane simulation in a global model of chemistry and transport. Conducting a CH4 simulation requires a comprehensive set of interannual varying CH4 emission inventories as well as a year-to-year varying 3-D fields of concentrations of hydroxyl radicals (OH) that is the main sink for CH4. The first part of this thesis examines the OH interannual variation, using results from a "full-chemistry" simulation that accounts for interannual variations in emissions of the main O3 precursors (including carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons) as well as the year-to-year variation in meteorology (e.g. atmospheric water vapor content), lightning emissions, and overhead O3 column. We calculated a global OH concentration of 1.22×106 molec cm-3 averaged over the period. We find that global OH concentrations steadily increased during the early 90's by 8% and reached a maximum in 1997. Afterward, concentrations decrease by 5%. We find that changes in water vapor concentrations, anthropogenic emissions of CO and NOx, lightning NOx emissions, and overhead ozone column all play a role in driving the OH year-to-year variations. The relative contributions of these parameters depend on the latitudinal and altitudinal regions of the troposphere. We examine in particular the influence of the 1997-1998 ENSO on the global OH concentrations. We find that the 1997-1998 ENSO resulted in a large increase in OH in the tropical areas and in the extra-tropical areas of the northern hemisphere (largely driven by an increase in water vapor) while it leads to a decrease in OH in the extra-tropical region of the southern hemisphere (that results from changes in the transport pathways that bring CO in the most southern latitudes and deplete OH). Our results (in terms of OH variability) are in contradiction to those found by other methods, especially those using inverse modeling approaches that are based on methyl chloroform (CH3CCl3) observations. This may results from poorly constrained sources. We then seek to implement a comprehensive set of CH4 emissions in our global model. We used anthropogenic CH4 emission data set of anthropogenic emissions from the International Institute of Technology (IIASA) whose emissions vary between 250 and 290 Tg/year between 1990 and 2000. We estimated biomass burning emissions, derived from an inventory of the total annual biomass burned area and emission factors that we constrained with measurements of the isotopic composition of atmospheric methane. This results in a global emissions rate of 60 Tg/year, which is much stronger than most of previous studies. We also developed a wetland scheme that accounts for soil carbon content, wetland fraction areas, soil temperature and humidity (with the three latter parameters varying interannually) and we evaluated the wetland areas with satellite-based estimates. Our global wetland emissions amount to about 150 Tg/year. We find a global CH4 lifetime of 10.6 years, which is in the range of values reported in previous studies. Comparing our results with different set of measurements gives promising results. The model reproduces well the year-to-year variation even if it slightly overestimates concentrations after 2000. By conducting different set of sensitivity simulations, we investigated the role of different parameters on the CH4 variations. We find that the long-term trend in CH4 is driven by a competition between anthropogenic emissions and tropospheric decay. Peaks of growth rate are driven by biomass burning emissions and to a lesser extend, wetland emissions. We find that even if we used increasing anthropogenic emissions during the 90s (that is in contradiction with some previous studies), reconstructing the observed year-to-year variation of CH4 concentrations was possible if one considers an increasing in OH during the 90s.

EPFL2008

Design, Synthesis and Characterization of New Nanoparticle Stabilizers and Their Application in Catalysis

Ilaria Biondi

In recent years, a strong emphasis in research towards creating sustainable and environmental friendly chemical processes has propelled the development of novel types of catalytic systems that combine advantages from homogeneous and heterogeneous processes. In this respect, transition metal based nanoparticles, TM-NPs, are excellent candidates with properties that offer high efficiency, high selectivity and the possibility of recycling. However, due to the particularly small size, within the nanoscale, TM-NPs are generally only kinetically stable and must be supported or stabilized by molecular systems to prevent aggregation into larger, less active materials. The work presented herein concerns the design, synthesis, characterisation and the applications of new TM-NP protecting agents, which are based on polymers functionalized with components that compose ionic liquids, P-ILs. Specifically, these P-ILs feature a hydrophobic poly-norbornene framework prepared using Ring Opening Metathesis Polymerization, ROMP, with pendant imidazolium-based ionic liquid substituents that allow fine tuning of the polymer solubility by anion-exchange. In Chapter 2, an aqueous, soluble P-IL containing the 1,2-dimethylimidazolium methane-sulphonate substituent and its use in the synthesis of aqueous gold NP, GNP, solutions is described. These particular TM-NPs were characterized by UV-VIS spectroscopy and Transmission Electron Microscopy, TEM. Subsequently, the P-IL/GNP solutions were used to catalyse the reduction of p-nitrophenol and the hydrogenation of cinnamaldehyde, both reactions are found to exhibit excellent activity under mild conditions. In Chapter 3, the potential of aqueous P-IL stabilizers to transfer GNPs from water to hydrophobic ILs and organic solvents is demonstrated. Using an anion-exchange process, the phase change does not result in GNP aggregation, as confirmed by UV-VIS spectroscopy and TEM analysis. Moreover, the same P-ILs were used as a protecting agents for the synthesis of aqueous rhodium NPs, RhNPs, which have been applied in the catalytic hydrogenation of natural compounds, including limonene, cinnamaldehyde, citral and α- and β-ionones. Through anion-exchange, the aqueous P-IL stabilized RhNPs are readily transferred into hydrophobic ILs, then used as catalysts in the hydrogenation of styrene and limonene. The stabilized RhNPs exhibited good activity, even after recycling. X-ray Photoelectron Spectroscopy, XPS, analysis demonstrated conclusively that the anion exchange and phase transfer of the Rh/Au-NP-IL system. In Chapter 4, three P-ILs containing poly-oxy linker groups, strategically placed between the poly-norbornene framework and the ionic groups, are described. The linkers provide additional stabilization through steric stabilization and coordination via the ether functional groups. These P-ILs were used to stabilize aqueous GNPs, which were characterized by UV-VIS spectroscopy and TEM. Their application in the reduction of p-nitrophenol reduction was demonstrated. Preliminary studies on the stabilization mode of PILs shown that the polymers, despite the presence of ionic groups, can stabilize electrostatically stabilized aqueous GNPs which otherwise aggregate in presence of water soluble imidazolium-based ILs. Moreover, they display good efficiency in terms of steric stabilization, comparable to systems featuring the poly-vinylpyrrolidone, PVP.

EPFL2011

Modeling study of the interannual variability in global tropospheric hydroxyl radical and methane concentrations over the last two decades

Jérôme Drevet

EPFL2008

Design, Synthesis and Characterization of New Nanoparticle Stabilizers and Their Application in Catalysis

Ilaria Biondi

EPFL2011