La criticité du réchauffement climatique incite à chercher des solutions pour réduire les émissions de dioxyde de carbone (CO₂). Le développement de catalyseurs qui peuvent aider à capturer, activer, réduire et valoriser le CO₂ est au cœur de ce défi. Cette thèse a répondu à cet appel en développant des mimétismes moléculaires inspirés de la Nature, dans le cadre plus large de la photosynthèse artificielle. Au début il s'agissait de suivre le parcours d'un photon de lumière visible et de déterminer comment il peut réduire la molécule de CO₂. Ensuite afin de réaliser des catalyseurs plus efficaces, de nouvelles molécules ont été synthétisées en s’inspirant de l’enzyme CO déshydrogénase (CODH) qui présente des performances exceptionnelles pour la réduction du CO₂. Enfin, une autre propriété du CODH a conduit à une validation de principe pour la valorisation immédiate du CO photo-produit dans la synthèse des liaisons amides marqués, une caractéristique courante des médicaments. / The criticality of global warming urges for the advancement of science to reduce carbon dioxide (CO₂) emissions in the atmosphere. At the heart of this challenge is the development of sustainable catalysts that can help capture, activate, reduce, and eventually valorize CO₂. This PhD work tried to respond to this call by developing molecular mimics inspired by natural systems in the larger scheme of artificial photosynthesis. Firstly, it involved tracking the journey of a photon of visible light and how it is transformed to a reducing power able to reduce CO₂. Secondly, in search for more efficient and stable catalysts, new mimics were synthesized inspired by the exceptional performance of CO dehydrogenase enzymes (CODH) in reducing CO₂. Lastly, further understanding of CODH also led to a proof-of-concept that directly valorizes the photo-produced CO for the synthesis of isotopically-labelled amide bonds, a common motif in pharmaceutically-relevant drugs.

Net photosynthesis, dark respiration, chlorophyll concentrations and growth were determined for Rumex patientia L. exposed to UV-B radiation corresponding to reduced atmospheric ozone concentrations. The hypothesis of whether reciprocity is maintained in the response of R. patientia to polychromatic UV-B radiation was tested. On the basis of the relationships derived from these studies, a simulation model was developed for the prediction of photosynthesis and growth of R. patientia exposed to UV-B radiation corresponding to any atmospheric ozone reduction. Photosynthetic rates were found to be depressed after two hours exposure to UV-B irradiance simulating a 0.18 atm•cm ozone column when the sun is at 30° from the zenith. During this initial exposure period, partial stomatal closure was implicated in the suppression of photosynthesis. However, after one day exposure, substantial increases in photosynthetic resistances apart from stomatal diffusion resistance occurred in the UV-irradiated plants and no differences in stomatal diffusion resistance were apparent between UV-irradiated and control plants. Dark respiration rates were slightly higher in those plants exposed to UV radiation. Leaf expansion of R. patientia was substantially repressed but only during the initial few days of exposure. Thereafter, leaf expansion was similar in the UV-irradiated and control plants. A reduction in total plant dry weight and leaf area of approximately 50 percent occurred after 22 days treatment while chlorophyll concentrations remained unaltered. Time of leaf initiation was shawm to be delayed in those plants exposed to UV-B radiation. Leaf longevity was decreased with increased UV radiation but accelerated whole-plant senescence and death was not observed. Photosynthetic rates determined through the ontogeny of the third leaf of R. patientia exposed to four levels of UV irradiance were found to be depressed as a function of the accumulated biologically effective UV irradiation. Thus, reciprocity was demonstrated between 6350 and 3175 J biologically effective UV irradiation. Results of the simultion model showed that under reduced atmospheric ozone concentrations, suppression of photosynthesis and leaf growth would be more severe during mid-sunnner (i . e. June) than would occur during the March to early May period, This results from smaller solar angles from the zenith and lower prevailing ozone concentrations prevalent during June. A validation test of the model was made with photosynthetic data obtained during a field study with R. patientia exposed to UV-B radiation corresponding to a 38 percent atmospheric ozone reduction (0.18 atm•cm when the sun was at 30° from the zenith). This validation test showed a reasonable correspondence between the measured and predicted photosynthetic rates. R. patientia was selected as the test species for this study because (1) it is reasonably sensitive to UV radiation as determined in preliminary studies evaluating approximately 20 native and agricultural plant species, (2) it is normally exposed to full sunlight in · its natural habitat, and (3) individual leaves are relatively long - lived (about 60 days) and are not normally shaded by other leaves of the same plant. Although this species probably represents one of the more sensitive plants to UV radiation, it would be this group of sensitive plants that would be initially affected under conditions of reduced atmospheric ozone. If more resistant plants with long-lived plant parts also accumulate UV radiation damage as was shown to occur in R. patientia, over sufficient periods of time even these species might be significantly impacted under conditions of reduced atmospheric ozone.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19781号 / 農博第2177号 / 新制||農||1041(附属図書館) / 学位論文||H28||N4997(農学部図書室) / 32817 / 京都大学大学院農学研究科農学専攻 / (主査)教授 白岩 立彦, 教授 奥本 裕, 教授 稲村 達也 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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Hurricane Katrina made landfall in 2005 damaging 1.2 billion cubic meters of timber including 48 million cubic meters of hardwood. An economically efficient method of artificial oak regeneration is necessary in many areas to restore this high value resource. Bareroot, conventional containerized, and EKOgrown® seedlings of Quercus shumardii and Q. texana were planted on two sites in south Mississippi. Growth and survival were evaluated for two years. Survival was assessed monthly and at the end of each growing season. Height and groundline diameter were assessed initially after planting and the end of each growing season. After two growing seasons, Q. Nuttallii exhibited superior performance generally when compared to Q. Shumardii. Conventional containerized had poor survival and initial growth likely caused by freeze damage in the nursery. EKOgrown® seedlings performed better than other planting stocks, however, high seedling cost makes them less cost-effective than bareroot seedlings which exhibited acceptable performance overall.

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The field of photochemistry is as innovative in development as it is broad in application. However, utilization of energy from the sun’s electromagnetic radiation remains secondary to the combustion of fossil fuels for the global energy consumption. This is neither a sustainable nor renewable system, and it has contributed to a major decline in the health of our global environment as the greenhouse gases emission has led to an incline in global temperatures and ocean acidity. To develop effective ways to utilize solar energy, experimental effort is being directed towards the understanding of photosensitizers, molecules which absorb solar radiation and initiate redox chemistry in CO2 reduction catalysts. Some zinc dipyrrins, one such class of photosensitizers, are theorized to undergo intersystem crossing through a charge separated state, a transition that is stabilized in polar solvents. This transition increases the lifetime of the excited state, as relaxation from the triplet state occurs much slower than from the singlet state. A phenyl substituted zinc dipyrrin was attempted to be synthesized and characterized using NMR spectroscopy to probe aromatic substituent effects on the molecule’s photophysics. The product was analyzed by UV-vis spectroscopy in order to confirm its purity and TLC analysis shows that the reaction kinetics are much slower in this phenyl substituted zinc dipyrrin than in previous reports, most likely due to the steric hindrance induced by the bulky phenyl substitutions.

Photokatalytische Systeme sind in der Lage, lichtinduziert kleine Moleküle zu aktivieren. Für diesen komplexen Katalysevorgang ist ein Zusammenspiel mehrerer Komponenten wichtig, wie dem Photosensibilisator (PS) und dem Katalysator. Im Rahmen der vorliegenden Dissertation wurde auf verschiedenen Wegen versucht, photokatalytische Systeme auf Basis von Rhenium und 3d-Metallen zu optimieren. So konnten neue Komplexe auf Rheniumbasis synthetisiert und charakterisiert werden, welche zugleich als Photosensibilisator sowie Katalysator fungieren. Die Komplexe zeigen dabei nicht nur eine höhere Absorption, sondern auch eine höhere katalytische Produktivität, als deren mononuklearer Verwandte. Mittels DFT-Rechnungen und spektroskopischen Untersuchungen konnte gezeigt werden, dass ein kooperativer Vorgang stattfindet, bei dem eine Rheniumeinheit als PS, und eine als Katalysator agiert. Durch Zugabe eines externen PS konnte die katalytische Produktivität nochmals deutlich erhöht werden. Durch den zusätzlichen PS wird intermediär eine Rhenium-Rhenium-Spezies ausgebildet, welche CO2 kooperativ über beide Rheniumeinheiten aktivieren kann. Neben literaturbekannten PS auf Iridiumbasis wurden zudem neuartige Kupferphotosensibilisatoren genutzt. Verschiedene Derivate des Kupferphotosensibilisators wurden in der CO2-Reduktion und H2-Produktion getestet. Es zeigte sich, dass verschiedene elektronische Eigenschaften der PS Auswirkungen auf die Katalyseproduktivität haben. Zusätzlich wurden Katalysatoren auf Basis von 3d-Metallen konzipiert, welche abhängig von einem zusätzlichen PS sind. Bestrahlungsexperimente mit Iridium- und Kupfer-PS wurden durchgeführt und somit die Produktivität der einzelnen Katalysatoren bestimmt. Es konnte gezeigt werden, dass sowohl die Wahl des Liganden, als auch des Katalysatormetalls Einfluss auf Menge und Selektivität der Produkte hat. / Photocatalytic systems are capable of light-induced activation of small molecules. Among other things, this allows CO2 to be reduced to higher-energetic molecules. The interaction of several components, such as the photosensitizer (PS) and the catalyst, is important for this complex catalysis process. In this dissertation, attempts were made to optimize systems based on rhenium and 3d metals in various ways. One approach was to synthesize and characterize new rhenium-based complexes, which can act as PSs and catalysts at the same time. The complexes showed not only higher absorption but also higher catalytic activity than their mononuclear relative. Using DFT calculations and spectroscopic investigations, it was shown that a cooperative process takes place, in which one rhenium unit acts as a PS and one as a catalyst. By adding an external PS, the activity was significantly increased again. This forms a rhenium-rhenium species which is able to activate CO2 cooperatively via both rhenium units. In addition to iridium-based PS known from the literature, novel copper photosensitizers were also used for this purpose. In order to get a better understanding of the interaction of both components, different derivatives of the copper photosensitizer were tested in the activity towards CO2 reduction and H2 evolution reaction. The electronic influence of the PS on the catalytic activity could be elucidated by means of Stern-Vollmer quenching studies and DFT calculations. In addition, catalysts based on 3d metals were designed. Iron, cobalt and nickel were used as the central atom together with two different macrocyclic ligands. These monomolecular compounds are dependent on a PS. Furthermore, irradiation experiments with iridium and copper PS were carried out and the activity of the individual catalysts was thereby determined. It was shown that the choice of the ligand as well as the catalyst has an influence on the quantity and selectivity of the resulting products.

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