Développer de nouvelles sources d’énergie respectueuses de l’environnement est un des enjeux majeur de nos sociétés développées. Pour espérer la pérennité de notre espèce sur cette planète, il est indispensable de développer les sources d'énergie renouvelable ; permettant de nous affranchir de la dépendance aux énergies fossiles polluantes et dont les stocks s’épuisent. Il appartient aux scientifiques d’apporter leurs contributions à cet important défi que l’on appelle la transition énergétique et pour ça d’aider à développer une énergie idéale qui ne produirait pas de déchet polluant, serait très efficace et largement disponible. L'énergie solaire représente un excellent candidat car elle est de loin la plus abondante et prometteuse source d’énergie propre. D'importants efforts sont donc menés pour développer les technologies solaires, notamment la photosynthèse artificielle.La photosynthèse artificielle a vu le jour il y a une centaine d’années et fait l’objet de beaucoup d’intérêt et de recherche. Cette technologie cherche à imiter la photosynthèse naturelle réalisée par les plantes; et cela afin de stocker l’énergie provenant du Soleil dans des composés utilisables par l’Homme. La photosynthèse artificielle consiste en l’élaboration de systèmes synthétiques capables sous impulsion lumineuse de réaliser la décomposition de l’eau de manière catalytique, pour générer du dihydrogène ou des produits issus de la réduction du CO2, que l’on appelle combustibles solaires car à haut potentiel énergétique. En effet, la photosynthèse débute par la photo-catalyse de l’oxydation de l’eau, qui permet d’extirper les électrons et les protons des molécules d’eau. Ce sont ces électrons et protons qui seront utilisés par un catalyseur pour produire les combustibles solaires.Depuis peu, une véritable volonté de comprendre les mécanismes qui ont lieu lors de ces réactions catalysées semble apparaitre. Ces réactions mettent en jeu des transferts électroniques multiples photo-induits et cela rend leur étude assez compliquée. Grâce à des avancées technologiques importantes, nous avons étudié de manière plus approfondies plusieurs systèmes photo-catalytiques afin d’en tirer des savoirs permettant de rationaliser le design et d’améliorer les capacités des futurs systèmes développés. Ces avancées techniques ont été possibles grâce à des collaborations interdisciplinaires entre des chimistes et des physiciens et ont permis de développer un montage d’absorption transitoire « double-pump» afin de caractériser les espèces transitoires formées et de retracer les mécanismes lors de deux transferts électroniques photo-induits successifs.Dans la seconde partie de ce travail, de nouveaux catalyseurs ont été développé pour la réaction de photo-catalyse de l’oxydation de l’eau. La majorité des études menées jusqu’ici sur le sujet ont porté sur des systèmes moléculaires, mais le manque de robustesse et de réutilisabilité des catalyseurs homogènes a poussé la recherche vers le domaine des matériaux. Ainsi depuis une quarantaine d’années des systèmes photo-catalytiques hétérogènes ont été développé. Nous avons explorés deux types de matériaux, des nanoparticules catalyseurs dans des systèmes photo-catalytiques, et des polymères qui à eux seuls sont capables de réaliser l’ensemble des fonctions nécessaires à la photo-catalyse d’une réaction telle que l’oxydation de l’eau sous irradiation de lumière visible.Ainsi au cours de cette thèse nous avons tenté par deux approches d’avancer les connaissances et le développement de la photosynthèse artificielle. Une solution encore peu développée au problème énergétique auquel notre société fait face est le recours aux combustibles solaires, et il est grand temps que la recherche avance et que la transition énergétique s’impose plus efficacement et largement. / Developpment of environment-friendly sources of energy is one of the stakes major for our societies. To hope for the sustainability of Humans on Earth, it is essential to change our consumer habits on energetics by breaking our dependance on fossil fuels, which use leads to ecological desasters and which stocks are running out. The key of this important challenge is the growth of renewable energy sources, and this is called energy transition. The ideal energy would not produce any polluting waste, would be efficient and widely available. Solar energy is an excellent candidate because it is by far the most abundant and promising source of clean energy. Thus, important efforts are made to developp the solar technologies, including artificial photosynthesis.Artificial photosynthesis was created a century ago and is the focus of many interests and researchs. This technology aims at mimicking the natural photosynthesis realized by plants ; and that in order to store the energy coming from the Sun irriadiation in compounds that can be used at demand. Artificial photosynthesis consists in the elaboration of synthetic systems able under light impulsion to realize the water splitting/decomposition reactions in a catalytique way, generating hydrogène or CO2 reduction products, which are called solar fuels thanks to their high energetic potentials. Indeed, photosynthesis begins with the photo-catalysis of water oxidation, which extirpates the electrons and protons of water molecules. And it is these electrons and protons which will be used to produce the solar fuels.Recently, a real commitment to understand deaply the mechanisms that take place during these catalysed reactions seems to appear. These transformations involve multiple photo-induced electron transfers and it returns their study relatively complicated. Thanks to technological breakthroughs, we studied in a thorough way several photocatalytic systems to draw knowledges ; allowing the rationalisation of the design and then the efficiency improvement of future developped systems. These technical advances were possible thanks to interdisciplinary collaborations between chemists and physicists and led to the developpment of a set-up of « double-pump » transient absorption, that enables to characterize the transient species formed and to track down the pathways during two successive photoinduced electron transfers.In the second part of this work, new catalysts were developped for the photocatalysis of water oxidation reaction. The big majority of the studies led so far on this subject concerned molecular systems, but the lack of robustness and reusability of homogeneous catalysts pushed the research towards materials area. Since about forty years, heterogeneous systems were developped for photocatalysis of several reactions. We explored two types of materials, nanoparticules as catalyst in photocatalytic systems ; and polymers that are able on their own to realize all the functions required for the photocatalysis of a reaction such as water oxidation under visible light irradiation.Thus, during this PhD we tried by two approaches to increase the knowledges and the development of artificial photosynthesis. A solution that is still under-developped to fix the energetic issue our society is facing to, is the use of solar fuels ; and it’s imperative for the research to move forward and that energy transition prevails more effectively and widely.

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.

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