Hydroxyamidinates et polymères de coordination : suspicions et valences mixtes

Dans un contexte où l’énergie représente un enjeu majeur pour les pays et organisations à économies émergentes et développées, la recherche de nouvelles sources renouvelables et la démocratisation des vecteurs énergétiques permettant l’approvisionnement mondial de façon durable constitue un devoir pour la communauté scientifique internationale. D’ailleurs, il serait essentiel que les nombreuses disciplines de la chimie concertent leurs efforts. Plus particulièrement, la croissance de la recherche en chimie de coordination orientée vers la photosynthèse artificielle ainsi que le développement de matériaux fonctionnels démontre l’importance indéniable de ce champ de recherche. Ce travail présente dans un premier temps l’étude des différentes voies de synthèse d’hydroxyamidines, un ligand chélatant aux propriétés de coordination prometteuses ne recevant que très peu d’attention de la part de la communauté scientifique. Dans un deuxième temps, nous présenterons le développement d’une stratégie d’assemblage de leurs complexes supramoléculaires impliquant des métaux de transition abondants et peu dispendieux de la première rangée. Dans un troisième temps, il sera question de l’investigation de leurs propriétés photophysiques et électrochimiques à des fins d’applications au sein de matériaux fonctionnels. Pour ce faire, les différentes voies de synthèse des hydroxyamidines et de leurs amidines correspondantes qui ont précédemment été étudiées par les membres du groupe seront tout d’abord perfectionnées, puis investiguées afin de déterminer leur versatilité. Ensuite, les propriétés de complexation des amox résultantes comportant des motifs sélectionnés seront déterminées pour enfin étudier les propriétés photophysiques et électrochimiques d’une série de complexes de métaux de transition de la première rangée. En somme, plusieurs designs qu’offrent les amox et bis-amox sont étudiés et les propriétés des architectures résultantes de leur auto-assemblage sont déterminées.

The distribution of meiofauna in surface sediments of the Fladen Ground, North Sea

A general study of structure, biomass, and dynamic estimates on meiofauna was carried out during PREFLEX (1975) and FLEX (1976), in 117- 141 m water depth. On the basis of these data an attempt was made to estimate meiofauna production, and this is discussed in relation to the energy input from the spring phytoplankton bloom. Sampling was performed at five stations, but only the stations 1, 4, and 5 were covered by a complete series from August 1975 to July 1976. At each station, from four replicate box core samples, two were withdrawn to study the abundance, distribution, and biomass of meiofauna, the content of chloroplastic pigment equivalents (CPE), and chemical and grain size analyses. At all stations grain size fell in the range of fine sand having median diameters (MD) of < 125 µm. From station 1 to 5 an increase in MD was observed. Highest values of CPE (7.81 µg m l**-1) and organic matter (4.7 %) were obtained in June and July (1976)/ August (1975), respectively. Meiofauna abundance was fairly uniform at all stations examined. Station 1 displayed maximal numbers during the whole investigation period. The abundance per 100 cm**2 varied between 15,550 and 34,900 organisms. All meiofauna studied both in total and as separate taxa showed annual cycles of abundance. Low abundance values were recorded during early summer, and maximum values during winter. High numbers of Foraminifera were obtained for August 1975 (9,460 per 100 cm**2) and July 1976 (9,710 per 100 cm**2). From December to June the values decreased from 3,280 to 1,030 per 100 cm**2. At station 1 maximum values of meiofauna biomass were recorded ranging from 1.5 to 2.7 g DWT m**-2. The mean meiofauna dry weight amounted to 2.1 g DWT m**-2. Based on minimum production, the P/B ratio for the area of station 1 might have a mean of 1.4. Taking into consideration generation times we believe that a turnover ratio of 2 is a conservative value for the Fladen Ground meiofauna. The annual production would amount to 4.2 g DWT m**-2 yr**-1. This is 27.5 % of the energy supply during the spring phytoplankton bloom, which is channelled into the meiofauna. The hypothesis is put forward that the energetic strategy of deep offshore meiofauna differs distinctively from that of shallow inshore meiofauna. While the shallow inshore meiofauna show a relatively fast response to organic matter input, the deep offshore meiofauna reacts much more slowly, the food energy consumption seems to be spread out over a longer period.

A novel methodology for analysis of large scale interconnected power and gas systems

The European Union continues to exert a large influence on the direction of member states energy policy. The 2020 targets for renewable energy integration have had significant impact on the operation of current power systems, forcing a rapid change from fossil fuel dominated systems to those with high levels of renewable power. Additionally, the overarching aim of an internal energy market throughout Europe has and will continue to place importance on multi-jurisdictional co-operation regarding energy supply. Combining these renewable energy and multi-jurisdictional supply goals results in a complicated multi-vector energy system, where the understanding of interactions between fossil fuels, renewable energy, interconnection and economic power system operation is increasingly important. This paper provides a novel and systematic methodology to fully understand the changing dynamics of interconnected energy systems from a gas and power perspective. A fully realistic unit commitment and economic dispatch model of the 2030 power systems in Great Britain and Ireland, combined with a representative gas transmission energy flow model is developed. The importance of multi-jurisdictional integrated energy system operation in one of the most strategically important renewable energy regions is demonstrated.

Peat Bog Ecosystems: Atmospheric pollution

Peatlands can be damaged by deposition of pollutants from the atmosphere – often termed ‘ acid rain ’ . This results from the release of sulphur and nitrogen pollutants into the atmosphere . Originally associated with the Industrial Revolution, ‘acid rain’ was first described by Robert Angus Smith, a Manchester chemist of the 1800s , whose obser vations were made in close proximity to the peatlands of the South Pennines. Sulphur dioxide (SO 2 ) pollution, which is mainly emitted from coal burning power stations, peaked in the 1970s and has since decreased by over 90% due to emission controls and ch anges in energy supply. N itrogen ous air pollutants have decreased less . N itrogen oxide (NO x ) emissions , which are mainly from vehicle s , have decreased by two thirds since their peak in 1990 , but the decrease in ammonia ( NH 3 ) emissions , which are mainly from intensive livestock farming, is much less certain and may be only about 20%.

Hydroxyamidinates et polymères de coordination : suspicions et valences mixtes

Dans un contexte où l’énergie représente un enjeu majeur pour les pays et organisations à économies émergentes et développées, la recherche de nouvelles sources renouvelables et la démocratisation des vecteurs énergétiques permettant l’approvisionnement mondial de façon durable constitue un devoir pour la communauté scientifique internationale. D’ailleurs, il serait essentiel que les nombreuses disciplines de la chimie concertent leurs efforts. Plus particulièrement, la croissance de la recherche en chimie de coordination orientée vers la photosynthèse artificielle ainsi que le développement de matériaux fonctionnels démontre l’importance indéniable de ce champ de recherche. Ce travail présente dans un premier temps l’étude des différentes voies de synthèse d’hydroxyamidines, un ligand chélatant aux propriétés de coordination prometteuses ne recevant que très peu d’attention de la part de la communauté scientifique. Dans un deuxième temps, nous présenterons le développement d’une stratégie d’assemblage de leurs complexes supramoléculaires impliquant des métaux de transition abondants et peu dispendieux de la première rangée. Dans un troisième temps, il sera question de l’investigation de leurs propriétés photophysiques et électrochimiques à des fins d’applications au sein de matériaux fonctionnels. Pour ce faire, les différentes voies de synthèse des hydroxyamidines et de leurs amidines correspondantes qui ont précédemment été étudiées par les membres du groupe seront tout d’abord perfectionnées, puis investiguées afin de déterminer leur versatilité. Ensuite, les propriétés de complexation des amox résultantes comportant des motifs sélectionnés seront déterminées pour enfin étudier les propriétés photophysiques et électrochimiques d’une série de complexes de métaux de transition de la première rangée. En somme, plusieurs designs qu’offrent les amox et bis-amox sont étudiés et les propriétés des architectures résultantes de leur auto-assemblage sont déterminées.

Análise do monitoramento de descargas atmosféricas na área de concessão da companhia força e luz do oeste em Guarapuava, Estado do Paraná

Aiming to analyze the monitoring of the atmospheric discharges incidence, the concession area of Companhia Forca e Luz do Oeste (CFLO) - Western Power and Light Company, located in the district of Guarapuava, state of Parana was chosen for a study developed in 2003, from January to December. After the air masses dynamics description, it was possible to identify the occurrence of atmospheric discharges and to compare them to the energy interruptions. To that end, atmospheric discharges density maps were created within the CFLO concession area for a later analysis of their influence in the electric energy supply. The monitoring of the atmospheric discharges and the comparison between this phenomenon and the occurrence of interruptions in the electric energy supply enabled this study. Results showed that such events are directly related, and that the rural area of the region under study underwent a major interference.

Fueling growth when oil peaks: directed technological change and the limits to efficiency

While fossil energy dependency has declined and energy supply has grown in the postwar world economy, future resource scarcity could cast its shadow on world economic growth soon if energy markets are forward looking. We develop an endogenous growth model that reconciles the current aggregate trends in energy use and productivity growth with the intertemporal dynamics of forward looking resource markets. Combining scarcity-rent driven energy supply (in the spirit of Hotelling) with profit-driven Directed Technical Change (in the spirit of Romer/Acemoglu), we generate transitional dynamics that can be qualitatively calibrated to current trends. The long-run properties of the model are studied to examine whether current trends are sustainable. We highlight the role of extraction costs in mining.

Análise proteômica de Chromobacterium violaceum: acúmulo estacionário e diferencial após exposição à luz UVC

Chromobacterium violaceum is a free-living bacillus, Gram-negative commonly found in water and sand of tropical and subtropical regions. One of its main characteristic it's the ability to produce the purple pigment named violacein, that shows countless biological activities. In 2003, the genome of this organism was totally sequenced and revealed important informations about the physiology of this bacteria. However, few post-genomics studies had been accomplished. This work evaluated the protein profile of C. violaceum cultivated in LB medium at 28ºC that allowed the identification and characterization of proteins related to a possible secretion system that wasn't identified and characterized yet in C. violaceum, to the quorum sensing system, to regulatory process of transcription and translation, stress adaptation and biotechnological potential. Moreover, the response of the bacteria to UVC radiation was evaluated. The comparison of the protein profile, analyzed through 2-D electrophoresis, of the control group versus the treatment group allowed the identification of 52 proteins that arose after stress induction. The obtained results enable the elaboration of a stress response pathway in C. violaceum generated by the UVC light. This pathway, that seems to be a general stress response, involves the expression of proteins related to cellular division, purine and pirimidine metabolism, heat chock or chaperones, energy supply, regulation of biofilm formation, transport, regulation of lytic cycle of bacteriophages, besides proteins that show undefined function. Despite the response present similarities with the classic SOS response of E. coli, we still cannot assert that C. violaceum shows a SOS-like response, mainly due to the absence of characterization of a LexA-like protein in this organism

Análisis de las simulaciones del proceso de deshidratación del gas natural con Aspen Hysys y Aspen Plus

El gas natural ha tomado un rol estratégico importante en el suministro de energía a nivel mundial como consecuencia de la creciente demanda global de energía. El agua es probablemente el componente indeseable más común en el gas natural no tratado ya que su presencia puede ocasionar la formación de hidratos y problemas de corrosión. Debido a las potenciales consecuencias costosas, el gas debe ser sometido a procesos de acondicionamiento a fin de alcanzar las especificaciones requeridas para su venta, transporte hacia los centros de distribución y consumo final. En los últimos años, la simulación de procesos está jugando un papel muy importante en la industria del gas y petróleo como una herramienta adecuada y oportuna para el diseño, caracterización, optimización y monitoreo del funcionamiento de procesos industriales. En el presente trabajo se describe el desarrollo de dos simulaciones estacionarias del proceso de deshidratación de gas natural por absorción con trietilenglicol (TEG), empleando los simuladores comerciales de procesos Aspen HYSYS V8.3 y Aspen PLUS V8.2. La composición del gas natural, la configuración del proceso y las condiciones de operación empleadas en los cálculos y la simulación son típicas de los yacimientos y plantas de acondicionamiento de la provincia de Salta (Argentina).

Induction of Microalgal Lipids for Biodiesel Production in Tandem with Sequestration of High Carbon Dioxide Concentration

There is no doubt that sufficient energy supply is indispensable for the fulfillment of our fossil fuel crises in a stainable fashion. There have been many attempts in deriving biodiesel fuel from different bioenergy crops including corn, canola, soybean, palm, sugar cane and vegetable oil. However, there are some significant challenges, including depleting feedstock supplies, land use change impacts and food use competition, which lead to high prices and inability to completely displace fossil fuel [1-2]. In recent years, use of microalgae as an alternative biodiesel feedstock has gained renewed interest as these fuels are becoming increasingly economically viable, renewable, and carbon-neutral energy sources. One reason for this renewed interest derives from its promising growth giving it the ability to meet global transport fuel demand constraints with fewer energy supplies without compromising the global food supply. In this study, Chlorella protothecoides microalgae were cultivated under different conditions to produce high-yield biomass with high lipid content which would be converted into biodiesel fuel in tandem with the mitigation of high carbon dioxide concentration. The effects of CO2 using atmospheric and 15% CO2 concentration and light intensity of 35 and 140 µmol m-2s-1 on the microalgae growth and lipid induction were studied. The approach used was to culture microalgal Chlorella protothecoides with inoculation of 1×105 cells/ml in a 250-ml Erlenmeyer flask, irradiated with cool white fluorescent light at ambient temperature. Using these conditions we were able to determine the most suitable operating conditions for cultivating the green microalgae to produce high biomass and lipids. Nile red dye was used as a hydrophobic fluorescent probe to detect the induced intracellular lipids. Also, gas chromatograph mass spectroscopy was used to determine the CO2 concentrations in each culture flask using the closed continuous loop system. The goal was to study how the 15% CO2 concentration was being used up by the microalgae during cultivation. The results show that the condition of high light intensity of 140 µmol m-2s-1 with 15% CO2 concentration obtain high cell concentration of 7 x 105 cells mL-1 after culturing Chlorella protothecoides for 9 to 10 day in both open and closed systems respectively. Higher lipid content was estimated as indicated by fluorescence intensity with 1.3 to 2.5 times CO2 reduction emitted by power plants. The particle size of Chlorella protothecoides increased as well due to induction of lipid accumulation by the cells when culture under these condition (140 µmol m-2s-1 with 15% CO2 concentration).

Biological analysis of the in-vitro effects of homologous recombination inhibition and its use in cancer treatment through synthetic lethality

Synthetic lethality represents an anticancer strategy that targets tumor specific gene defects. One of the most studied application is the use of PARP inhibitors (e.g. olaparib) in BRCA1/2-less cancer cells. In BRCA2-defective tumors, olaparib (OLA) inhibits DNA single-strand break repair, while BRCA2 mutations hamper homologous recombination (HR) repair. The simultaneous impairment of those pathways leads BRCA-less cells to death by synthetic lethality. The projects described in this thesis were aimed at extending the use of OLA in cancer cells that do not carry a mutation in BRCA2 by combining this drug with compounds that could mimic a BRCA-less environment via HR inhibition. We demonstrated the effectiveness of our “fully small-molecule induced synthetic lethality” by using two different approaches. In the direct approach (Project A), we identified a series of neo-synthesized compounds (named RAD51-BRCA2 disruptors) that mimic BRCA2 mutations by disrupting the RAD51-BRCA2 interaction and thus the HR pathway. Compound ARN 24089 inhibited HR in human pancreatic adenocarcinoma cell line and triggered synthetic lethality by synergizing with OLA. Interestingly, the observed synthetic lethality was triggered by tackling two biochemically different mechanisms: enzyme inhibition (PARP) and protein-protein disruption (RAD51-BRCA2). In the indirect approach (Project B), we inhibited HR by interfering with the cellular metabolism through inhibition of LDH activity. The obtained data suggest an LDH-mediated control on HR that can be exerted by regulating either the energy supply needed to this repair mechanism or the expression level of genes involved in DNA repair. LDH inhibition also succeeded in increasing the efficiency of OLA in BRCA-proficient cell lines. Although preliminary, these results highlight a complex relationship between metabolic reactions and the control of DNA integrity. Both the described projects proved that our “fully small-molecule-induced synthetic lethality” approach could be an innovative approach to unmet oncological needs.

Development and optimization of fibre-shaped dye-sensitized solar cells employing an innovative fully organic sensitizer

The quality of human life depends to a large degree on the availability of energy. In recent years, photovoltaic technology has been growing extraordinarily as a suitable source of energy, as a consequence of the increasing concern over the impact of fossil fuels on climate change. Developing affordable and highly efficiently photovoltaic technologies is the ultimate goal in this direction. Dye-sensitized solar cells (DSSCs) offer an efficient and easily implementing technology for future energy supply. Compared to conventional silicon solar cells, they provide comparable power conversion efficiency at low material and manufacturing costs. In addition, DSSCs are able to harvest low-intensity light in diffuse illumination conditions and then represent one of the most promising alternatives to the traditional photovoltaic technology, even more when trying to move towards flexible and transparent portable devices. Among these, considering the increasing demand of modern electronics for small, portable and wearable integrated optoelectronic devices, Fibre Dye-Sensitized Solar Cells (FDSSCs) have gained increasing interest as suitable energy provision systems for the development of the next-generation of smart products, namely “electronic textiles” or “e-textiles”. In this thesis, several key parameters towards the optimization of FDSSCs based on inexpensive and abundant TiO2 as photoanode and a new innovative fully organic sensitizer were studied. In particular, the effect of various FDSSCs components on the device properties pertaining to the cell architecture in terms of photoanode oxide layer thickness, electrolytic system, cell length and electrodes substrates were examined. The photovoltaic performances of the as obtained FDSSCs were fully characterized. Finally, the metal part of the devices (wire substrate) was substituted with substrates suitable for the textile industry as a fundamental step towards commercial exploitation.

Progettazione, modellazione e integrazione di risorse rinnovabili per promuovere lo sfruttamento dell'energia da moto ondoso e la Blue Growth.

L’energia da onda potrebbe assumere un ruolo fondamentale per la transizione energetica durante i prossimi decenni, grazie alla sua continuità nel tempo molto superiore rispetto ad altre risorse rinnovabili e alla sua vasta distribuzione nello spazio. Tuttavia, l’energia da onda è ancora lontana dall’essere economicamente sostenibile, a causa di diverse problematiche tecnologiche e alle difficoltà finanziarie associate. In questa ricerca, si è innanzitutto affrontata una delle maggiori sfide tecniche, nello specifico la progettazione e modellazione di sistemi di ancoraggio per i dispositivi galleggianti, proponendo possibili soluzioni per la modellazione numerica di sistemi di ancoraggio complessi e per l’ottimizzazione dei dispositivi stessi. Successivamente sono state analizzate le possibili sinergie strategiche di installazioni per lo sfruttamento della energia da onda con altre risorse rinnovabili e la loro applicazione nel contesto di aree marine multiuso. In particolare, una metodologia per la valutazione della combinazione ottimale delle risorse rinnovabili è stata sviluppata e verificata in due diversi casi studio: un’isola e una piattaforma offshore. Si è così potuto evidenziare l’importante contributo della risorsa ondosa per la continuità energetica e per la riduzione della necessità di accumulo. Inoltre, è stato concepito un metodo di supporto decisionale multicriteriale per la valutazione delle opzioni di riuso delle piattaforme offshore alla fine della loro vita operativa, come alternativa al decommissionamento, nell’ottica di una gestione sostenibile e della ottimizzazione dell’uso dello spazio marino. Sulla base dei criteri selezionati, l’inclusione di attività innovative come la produzione di energia da onda si è dimostrata essere rilevante per rendere vantaggioso il riuso rispetto al decommissionamento. Numerosi studi recenti hanno infatti sottolineato che, nell’ambito della “crescita blu”, i mercati come l’oil&gas, le attività offshore e le isole stimoleranno lo sviluppo di tecnologie innovative come lo sfruttamento dell’energia da onda, promuovendo la sperimentazione e fornendo un importante contributo all’avanzamento tecnico e alla commercializzazione.

Development of processes for the valorization of lignocellulosic biomass based on renewable energies

The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.

Experimental characterization of hydrogen containing flames

The current environmental and socio-economic situation promotes the development of carbon-neutral and sustainable solutions for energy supply. In this framework, the use of hydrogen has been largely indicated as a promising alternative. However, safety aspects are of concern for storage and transportation technologies. Indeed, the current know-how promotes its transportation via pipeline as compressed gas. However, the peculiar properties of hydrogen make the selection of suitable materials challenging. For these reasons, dilution with less reactive species has been considered a short and medium solution. As a way of example, methane-hydrogen mixtures are currently transported via pipelines. In this case, the hydrogen content is limited to 20% in volume, thus keeping the dependence on natural gas sources. On the contrary, hydrogen can be conveniently transported by mixing it with carbon dioxide deriving from carbon capture and storage technologies. In this sense, the interactions between hydrogen and carbon dioxide have been poorly studied. In particular, the effects of composition and operative conditions in the case of accidental release or for direct use in the energy supply chain are unknown. For these reasons, the present work was devoted to the characterization of the chemical phenomena ruling the system. To this aim, laminar flames containing hydrogen and carbon dioxide in the air were investigated experimentally and numerically. Different detailed kinetic mechanisms largely validated were considered at this stage. Significant discrepancies were observed among numerical and experimental data, especially once a fuel consisting of 40%v of hydrogen was studied. This deviation was attributed to the formation of a cellular flame increasing the overall reactivity. Hence, this observation suggests the need for combined models accounting for peculiar physical phenomena and detailed kinetic mechanisms characterizing the hydrogen-containing flames.