Artificial systems involving water oxidation and solar cells are promising ways for the conversion of solar energy into fuels and electricity. These systems usually consist of a photosensitizer, an electron donor and / or an electron acceptor. This thesis deals with the synthesis and photoinduced electron transfer of several donor-sensitizer-acceptor supramolecular systems. The first part of this thesis describes the synthesis and properties of two novel dinuclear ruthenium complexes as electron donors to mimic the donor side reaction of Photosystem II. These two Ru2 complexes were then covalently linked to ruthenium trisbipyridine and the properties of the resulting trinuclear complexes were studied by cyclic voltammetry and transient absorption spectroscopy. The second part presents the synthesis and photoinduced electron transfer of covalently linked donor-sensitizer supramolecular systems in the presence of TiO2 as electron acceptors. Electron donors are tyrosine, phenol and their derivatives, and dinuclear ruthenium complexes. Intramolecular electron transfer from the donor to the oxidized sensitizer was observed by transient absorption spectroscopy after light excitation of the Ru(bpy)32+ moiety. The potential applications of Ru2-based electron donors in artificial systems for water oxidation and solar cells are discussed. In the final part, the photoinduced interfacial electron transfer in the systems based on carotenoids and TiO2 is studied. Carotenoids are shown to act as both sensitizers and electron donors, which could be used in artificial systems to mimic the electron transfer chain in natural photosynthesis.

The Small Cab-like Proteins (SCPs) in the cyanobacterium Synechocystis sp. PCC 6803 accumulate in cells grown under different stress conditions. Genes coding for SCPs have been found in all sequenced organisms performing oxygenic photosynthesis and even in the genomes of cyanophages. Deletion of multiple scp genes in Synechocystis resulted in mutants with severely impaired growth and altered pigment content. These findings indicate the importance of SCPs in photosynthesis; however, their specific function is not well understood. SCPs share a chlorophyll-binding motif with the plant light harvesting complex, suggesting that they bind chlorophyll. Here I describe my findings, which unambiguously show that SCPs are able to bind chlorophyll in vitro. Although they affect both the stoichiometric ratio of Photosystem I to II and chlorophyll stability, they do not seem to be directly involved in non-photochemical quenching. I was able to reveal the location of the SCPs within the cyanobacterial cell: in stressed cells they attach to Photosystem II in the thylakoid membrane. Furthermore, I revealed the presence of another light-harvesting like (Lil)/SCP protein in Synechocystis sp. PCC 6803. The gene, slr1544, codifying for this newly characterised LilA protein, co-transcribes together with scpD and also appears to bind to Photosystem II during stress.

The objective of this thesis is to investigate the photocatalytic activity in nanosized TiO2 structures. Two different structures were used for two different reaction systems. In the first part of the study, TiO2 coated on glass beads by a sol-gel procedure were used to test the photocatalytic CO2 reduction reaction with H2O and H2 in the gas phase. The results of photocatalytic CO2 reduction reaction revealed that CO2 reduction step of the overall reaction proceeds in dark / while illumination is required for water splitting reaction. In the second part of the study, Photocatalytic oxidation activity of the commercial TiO2 powders mixed with grout and plaster were studied for a potential commercial self cleaning material. A method based on gas phase benzene oxidation was developed for testing TiO2 added cement based self cleaning surfaces. This method was used to screen 15 commercial TiO2 samples with and without cement. Based on this method a commercial TiO2 sample (S9) was selected for further use. Surface of 15 commercial TiO2 samples were characterized by using NO and CO2 as probe molecules. Photocatalytic benzene oxidation experiments showed that using TiO2 on the surface lead to more effective surfaces in terms of photocatalytic activity. TiO2 was bound to surface by inorganic materials without much activity loss. This kind of amount optimization is of commercial importance.

The sacoglossan sea slug Elysia clarki is able to photosynthesize for three to four months using chloroplasts sequestered from its algal food sources. Furthermore, the slug is able to store multiple chloroplasts from different algal species within the same cell. This research, consisting of several related studies, explores the role that provision of organic nutrients via photosynthesis plays in the biology of the slug. The first chapter demonstrates that, under conditions of starvation, photosynthetic activity in E. clarki remains fully functional for one month after which it then declines. During the first month of starvation the slug exhibits similar feeding behavior as slugs provided a continuous supply of food, suggesting that photosynthesis delays the onset of starvation-induced behavioral changes. The second chapter explores E. clarki's spatial relationships with algae known to be food sources in the field. In areas with high slug density, edible algal populations were very low. DNA barcoding was employed to demonstrate that the algae found near slugs were poor predictors of which foods were actually consumed by slugs. Generally, there was a mismatch between algae available in the field and slug diets. The third chapter explores how E. clarki is able to maintain photosynthesis. After labeling with a C14 ALA incubation process, then chlorophyll was extracted from slugs and purified using HPLC. Results indicate that recently collected E. clarki are able to synthesize chlorophyll, whereas slugs starved for 3 months were not. Photosynthesis plays a very important role for E. clarki and its relationships with food algae.

Anthropogenic activities are responsible for increases in atmospheric CO₂ and climate change. These increases are partly counterbalanced by natural processes, such as carbon uptake in land surfaces. These processes are themselves subject to climate change, creating a coupled carbon-climate system. I investigated the carbon sink that woody encroachment represents, using a Central Texas savanna as study site, and studied how climatic factors influence this carbon sink. Woody plant encroachment, a worldwide structural change in grassland and savanna ecosystems, alters many ecosystem properties, but the net effect on the carbon balance is uncertain. Woody encroachment represents one of the key uncertainties in the US carbon balance, and demands a more detailed understanding. To come to a process-based understanding of the encroachment effect on carbon dynamics, I analyzed patterns of carbon exchange using eddy-covariance technology. I expected the imbalance between carbon uptake and release processes associated with the encroaching trees specifically, to be responsible for the carbon sink. I also expected that the sink would vary in time, due to strong links between carbon fluxes and soil water in this semi-arid ecosystem. I further studied the ecophysiology of the dominant species, as well as soil respiration processes under different vegetation types, and scaled these findings in space and time. I found that the ecosystem was a significant carbon sink of 405 g C m⁻² yr⁻¹. The encroaching trees increased photosynthesis by 180% and decreased soil respiration by 14%, compared to the grassland, resulting in a strong carbon sink due to the encroachment process. The encroaching process also altered carbon dynamics in relation to climatic drivers. The evergreen species Ashe juniper effectively lengthened the growing season and widened the temperature range over which the ecosystem acts as a carbon sink. The drought resistance of the encroaching trees reduced the sensitivity of this savanna to drought. I conclude that encroachment in Central Texas savannas increased the carbon sink strength by increasing the carbon inputs into the ecosystem. Woody encroachment also reduced the sensitivity to climatic drivers. These two effects constitute a direct effect, as well as a negative feedback to the coupled carbon-climate system. / text

Aerosol particles affect the Earth’s climate, although their impact is associated with large uncertainties. Primary marine aerosol represents a significant fraction of the global aerosol budget considering the Earth’s 70-percentage coverage by oceans. They are produced when bubbles burst at the ocean surface and can consist of sea salt, organic matter and bacteria. An experimental approach was here used to investigate the primary marine aerosol production from the bubble-bursting mechanism using water from four different geographical locations. The main findings include: Similar and stable aerosol number size distributions at all locations, centered close to 0.2 μm. Largely varying aerosol organic fractions, both with size and location. Clear tendency for increased water temperature to negatively influence the aerosol production. No covariance between surface water chlorophyll α and aerosol production on a 10-minute time scale, although decreased aerosol production was observed at times of elevated phytoplankton activity on longer time scales. Mainly external mixtures of sea salt and organics was observed. A high tendency for colony-forming marine bacteria to use bubble-bursting to reach the atmosphere. A clear diurnal cycle in aerosol production was found for both laboratory produced aerosol and in-situ aerosol fluxes, probably biologically driven. The first near coastal sea spray fluxes with limited fetch and low salinity. While the primary marine aerosol spectral shape is stable, emission concentration varies with environmental parameters. Above that, the organic fraction of the aerosol varies largely between locations. This shows that observations of primary marine aerosol emissions not necessarily can be applied to large time- or spatial scales. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: In press. Paper 3: Manuscript. Paper 4: Manuscript.

A detailed understanding of natural photosynthesis provides inspiration for the development of sustainable and renewable energy sources, i.e. a technology that is capable of converting solar energy directly into chemical fuels. This concept is called artificial photosynthesis. The work described in this thesis contains contributions to the development of artificial photosynthesis in two separate areas. The first one relates to light harvesting with a focus on the question of how electronic properties of photosensitizers can be tuned to allow for efficient photo-induced electron transfer processes. The study is based on a series of bis(tridentate)ruthenium(II) polypyridyl complexes, the geometric properties of which make them highly appealing for the construction of linear donor-photosensitizer-acceptor arrangements for efficient vectorial photo-induced electron transfer reactions. The chromophores possess remarkably long lived 3MLCT excited states and it is shown that their excited-state oxidation strength can be altered by variations of the ligand scaffold over a remarkably large range of 900 mV. The second area of relevance to natural and artificial photosynthesis that is discussed in this thesis relates to the coupled movement of protons and electrons. The delicate interplay between these two charged particles regulates thermodynamic and kinetic aspects in many key elementary steps of natural photosynthesis, and further studies are needed to fully understand this concept. The studies are based on redox active phenols with intramolecular hydrogen bonds to quinolines. The compounds thus bear a strong resemblance to the tyrosine/histidine couple in photosystem II, i.e. the water-plastoquinone oxidoreductase enzyme in photosynthesis. The design of the biomimetic models is such that the distance between the proton donor and acceptor is varied, enabling studies on the effect the proton transfer distance has on the rate of proton-coupled electron transfer reactions. The results of the studies have implications for the development of artificial photosynthesis, in particular in connection with redox leveling, charge accumulation, as well as electron and proton transfer. In addition to these two contributions, the excited-state dynamics of the intramolecular hydrogen-bonded phenols was investigated, thereby revealing design principles for technological applications based on excited-state intramolecular proton transfer and photoinduced tautomerization.

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Mathematical modeling of biological systems is a powerful tool to systematically investigate the functions of biological processes and their relationship with the environment. To obtain accurate and biologically interpretable predictions, a modeling framework has to be devised whose assumptions best approximate the examined scenario and which copes with the trade-off of complexity of the underlying mathematical description: with attention to detail or high coverage. Correspondingly, the system can be examined in detail on a smaller scale or in a simplified manner on a larger scale. In this thesis, the role of photosynthesis and its related biochemical processes in the context of plant metabolism was dissected by employing modeling approaches ranging from kinetic to stoichiometric models. The Calvin-Benson cycle, as primary pathway of carbon fixation in C3 plants, is the initial step for producing starch and sucrose, necessary for plant growth. Based on an integrative analysis for model ranking applied on the largest compendium of (kinetic) models for the Calvin-Benson cycle, those suitable for development of metabolic engineering strategies were identified. Driven by the question why starch rather than sucrose is the predominant transitory carbon storage in higher plants, the metabolic costs for their synthesis were examined. The incorporation of the maintenance costs for the involved enzymes provided a model-based support for the preference of starch as transitory carbon storage, by only exploiting the stoichiometry of synthesis pathways. Many photosynthetic organisms have to cope with processes which compete with carbon fixation, such as photorespiration whose impact on plant metabolism is still controversial. A systematic model-oriented review provided a detailed assessment for the role of this pathway in inhibiting the rate of carbon fixation, bridging carbon and nitrogen metabolism, shaping the C1 metabolism, and influencing redox signal transduction. The demand of understanding photosynthesis in its metabolic context calls for the examination of the related processes of the primary carbon metabolism. To this end, the Arabidopsis core model was assembled via a bottom-up approach. This large-scale model can be used to simulate photoautotrophic biomass production, as an indicator for plant growth, under so-called optimal, carbon-limiting and nitrogen-limiting growth conditions. Finally, the introduced model was employed to investigate the effects of the environment, in particular, nitrogen, carbon and energy sources, on the metabolic behavior. This resulted in a purely stoichiometry-based explanation for the experimental evidence for preferred simultaneous acquisition of nitrogen in both forms, as nitrate and ammonium, for optimal growth in various plant species. The findings presented in this thesis provide new insights into plant system's behavior, further support existing opinions for which mounting experimental evidences arise, and posit novel hypotheses for further directed large-scale experiments. / Mathematische Modellierung biologischer Systeme eröffnet die Möglichkeit systematisch die Funktionsweise biologischer Prozesse und ihrer Wechselwirkungen mit der Umgebung zu untersuchen. Um präzise und biologisch relevante Vorhersagen treffen zu können, muss eine Modellierungsstrategie konzipiert werden, deren Annahmen das untersuchte Szenario bestmöglichst widerspiegelt und die dem Trade-off der Komplexität der zugrunde liegenden mathematischen Beschreibung gerecht wird: Detailtreue gegenüber Größe. Dementsprechend kann das System detailliert, in kleinerem Umfang oder in vereinfachter Darstellung im größeren Maßstab untersucht werden. In dieser Arbeit wird mittels verschiedener Modellierungsansätze, wie kinetischen und stöchiometrischen Modellen, die Rolle der Photosynthese und damit zusammenhängender biochemischer Prozesse im Rahmen des Pflanzenstoffwechsels analysiert. Der Calvin-Benson-Zyklus, als primärer Stoffwechselweg der Kohlenstofffixierung in C3-Pflanzen, ist der erste Schritt der Stärke- und Saccharoseproduktion, welche maßgeblich für das Wachstum von Pflanzen sind. Basierend auf einer integrativen Analyse zur Modellklassifizierung wurden aus der größten bekannten Sammlung von (kinetischen) Modellen des Calvin-Benson-Zyklus diejenigen ermittelt, die für die Entwicklung von Metabolic-Engineering-Strategien geeignet sind. Angeregt von der Fragestellung warum Kohlenstoff transitorisch vorwiegend in Form von Stärke anstatt Saccharose gespeichert wird, wurden die metabolischen Kosten beider Syntheseprozesse genauer betrachtet. Die Einbeziehung der Bereitstellungskosten der beteiligten Enzyme stützt die Tatsache, dass bevorzugt Stärke als temporärer Kohlenstoffspeicher dient. Die entprechende Untersuchung erfolgte einzig auf Grundlage der Stöchiometrie der Synthesewege. In vielen photosynthetisch-aktiven Organismen findet zudem Photorespiration statt, die der Kohlenstofffixierung entgegenwirkt. Die genaue Bedeutung der Photorespiration für den Pflanzenmetabolismus ist noch umstritten. Eine detaillierte Einschätzung der Rolle dieses Stoffwechselweges bezüglich der Inhibierung der Kohlenstofffixierungsrate, der Verknüpfung von Kohlenstoff- und Stickstoffmetabolismus, der Ausprägung des C1-Stoffwechsels sowie die Einflussnahme auf die Signaltransduktion wurde in einer modell-basierten, kritischen Analyse vorgenommen. Um die Photosynthese in ihrem metabolischen Kontext verstehen zu können, ist die Betrachtung der angrenzenden Prozesse des primären Kohlenstoffmetabolismus unverzichtbar. Hierzu wurde in einem Bottom-up Ansatz das Arabidopsis core Modell entworfen, mittels dessen die Biomasseproduktion, als Indikator für Pflanzenwachtum, unter photoautotrophen Bedingungen simuliert werden kann. Neben sogenannten optimalen Wachstumsbedingungen kann dieses großangelegte Modell auch kohlenstoff- und stickstofflimitierende Umweltbedingungen simulieren. Abschließend wurde das vorgestellte Modell zur Untersuchung von Umwelteinflüssen auf das Stoffwechselverhalten herangezogen, im speziellen verschiedene Stickstoff-, Kohlenstoff- und Energiequellen. Diese auschließlich auf der Stöchiometrie basierende Analyse bietet eine Erklärung für die bevorzugte, gleichzeitige Aufnahme von Nitrat und Ammonium, wie sie in verschiedenen Spezies für optimales Wachstum experimentell beobachtet wurde. Die Resultate dieser Arbeit liefern neue Einsichten in das Verhalten von pflanzlichen Systemen, stützen existierende Ansichten, für die zunehmend experimentelle Hinweise vorhanden sind, und postulieren neue Hypothesen für weiterführende großangelegte Experimente.

The purpose of this study was to investigate the effects of 5E learning cycle, conceptual change texts and traditional instruction on 8th grade students&amp / #8217 / understanding of photosynthesis and respiration in plants. Besides, the effect of instruction on students&amp / #8217 / attitudes toward science as a school subject was investigated. One hundred and one, 8th grade students from three classes of one elementary school in Ankara attended in this study. This study was carried out during the fall semester of 2003-2004 academic year. The classes were randomly assigned as control and experimental groups. Students in the first experimental group (n=33) received 5E learning cycle based instruction, the second experimental group (n=34) received conceptual change text based instruction and students in the control group (n=34) received traditional instruction. Two-tier multiple-choice diagnostic test, Photosynthesis and Respiration in Plants Concept Test, was used to determine students&amp / #8217 / understanding of photosynthesis and respiration in plants. The test was administered to the sample of the study as pre- and post-test. Students&amp / #8217 / attitudes toward science and their reasoning abilities were measured by Attitude Scale Toward Science and Test of Logical Thinking respectively. The hypotheses of the study were tested by using analysis of covariance (ANCOVA). The results indicated that there were significant differences among the treatment groups with respect to their understanding of photosynthesis and respiration in plants. Both 5E learning cycle based instruction and conceptual change text based instruction were found effective to eliminate 8th grade students&amp / #8217 / misconceptions about photosynthesis and respiration in plants. The results also showed that there were no significant differences among the treatment groups with respect to attitudes toward science as a school subject.