In natural oxygen-producing photosynthesis solar energy is stored as chemical energy, in carbohydrates, fats and amino acids, using water as electron source. The large transmembrane protein complex, PSII, is the key enzyme in the light-driven reactions. Water oxidation is accomplished by a triad in PSII in which the Mn-cluster plays an important role. In the artificial photosynthetic system, nature’s photosynthesis will be mimicked such that hydrogen, a sustainable energy source, can be produced from solar energy and water alone. Since water oxidiation requires the catalytic activity of a Mn-cluster in photosynthesis, different artificially constructed manganese complexes are investigated. The dinuclear ([Mn2(II,III)L(µ-OAc)2]ClO4), where L is the X-anion of 2-(N,N-Bis(2-methylpyridyl)aminomethyl)-6-(N-(3,5-ditert-butylbenzyl-2-hydroxy)-N-(pyridylmethyl)aminomethyl)-4-methylphenol, an unsymmetric ligand with two coordinating phenolate groups, has been studied. The two Mn-ions are linked via a mono-µ-oxo bridge and two acetate ligands. Q-band Electron Paramagnetic Resonance was conducted on the Unsymmetric Mn2(II,III) Complex. Aquired results show that the complex has a 2600 Gauss broad signal (11 400-14 000 Gauss) with 14-17 lines at g~2 and hyperfines of 120 Gauss. This is consistent with previous X-band studies. Q-band spectra of the Unsymmetric Mn(II,III) display increased hyperfine resolution compared to Qband spectra of the symmetric complex, Mn2(bpmp)(µ-OAC)2. This is noticeable since Unsymmetric Mn2(II,III) and Mn2 (bpmp)(µ-OAC)2 partly overlap in low-frequency experiments (X-band EPR). Further investigations are yet to be expected. Nevertheless, the conducted thesis study provides important knowledge in the futuristic goal of building an artificial super-complex.

Ball State University LibrariesLibrary services and resources for knowledge buildingMasters ThesesThere is no abstract available for this thesis.

Ball State University LibrariesLibrary services and resources for knowledge buildingMasters ThesesThere is no abstract available for this thesis.

It is well known that photosynthetic health impacts the overall fitness of the mature plant. This study aims to determine photosynthetic vigour of spring wheat cultivars during field development as well as their biomass composition at maturity to determine which cultivars/varieties would be optimum for cellulosic ethanol production. Additionally, specimens were grown at non-acclimating (20˚C), cold acclimating (5˚C), non-acclimating high CO2 (20˚C/750 µmol mol-1 CO2) and cold-acclimating high CO2 (5˚C/750 µmol mol-1 CO2) to resolve photosynthetic responses to different environments. Plants were photoinhibited under high irradiance (5 fold growth irradiance) and low temperature (5˚C) while photochemical efficiency of PSII was monitored throughout using chlorophyll fluorescence imaging. Vegetative production was monitored using normalised difference vegetation index. De-epoxidation of xanthophyll photoprotective pigments were also recorded using HPLC and photochemical reflectance index. Additionally, carbon assimilation rate was recorded with infra-red gas analysis methods. It was discovered that no one wheat cultivar demonstrated any photosynthetic advantage in the field or under photoinhibitory conditions. However, photosynthetic differences were observed between wheat grown in different environments. Plants that were cold-acclimated or grown under high CO2 were more resilient to photoinhibitory stress. This was also reflected by most cold-acclimated cultivars having increased triose phosphate utilization, electron transport and zeaxanthin induction. Plants acclimated to high CO2 at room temperature also displayed increased electron transport and triose phosphate utilization but had decreased zeaxanthin induction. It is hypothesized increased excitation pressure in cold acclimated and high CO2 cultivars allowed for their increase in the development of photoinhibitory tolerance.

Crown architecture affects tree growth through the control of leaf area and its display. Yet the linkages between crown structure, leaf traits, and productivity of elite selections of forest trees and responses to intensive silviculture are not fully understood. It was hypothesized that trees with crown and leaf traits governing efficient light capture and photosynthesis at the canopy scale would be the most productive. To this end, families of loblolly (Pinus taeda) and slash pine (Pinus elliottii) were grown at three experimental sites in the West Gulf Coastal Plain of Texas and Louisiana under two silvicultural treatments, including repeated fertilization with control of competing vegetation (HI), and a control (C) consisting of fertilization at planting. Families and species differed in crown traits and aboveground productivity, and genotype differences increased throughout the first 5 years of stand development. Crown shape was important for light interception and growth initially, but at the onset of canopy closure, crown size, stand leaf area and its distribution within crowns affected canopy light interception and tree growth. Among all families and treatments, aboveground biomass productivity was positively related to absorbed photosynthetically active radiation (APAR) and canopy photosynthesis. Light-use efficiency (ε) varied from 0.41 to 0.56 g MJ-1 among families and was lowest in slash pine. Variability in aboveground biomass growth was related more to stand leaf area and APAR than to differences in light-use efficiency in these young stands. Leaf physiological, chemical and morphological attributes changed within crowns in accordance with developing light availability gradients. Physiological attributes, such as net photosynthesis, were better predictors of family performance when integrated at the canopy level than leaf level in the examined pine species. Crown size, light absorption, and aboveground growth generally ranked higher in the HI treatment than in the control, although the effects of the intensive silvicultural treatments did not differ statistically. Family performance was independent of treatment. Crown and canopy attributes, such as high leaf area index and large crowns with low leaf area density per crown volume, may be useful in the selection of highly productive genotypes of loblolly and slash pine under intensive silviculture.

The aim of this study is to investigate and reveal challenges in photocatalytic CO2 reduction tests performed in liquid media. Effect of test conditions in photocatalytic studies are often underestimated with an assumption of negligible mass transfer limitations in observed rate results. In this study, effect of mass transfer limitations in liquid phase photocatalytic tests was revealed with stirring rate and gas hold-up time experiments performed with Pt/TiO2 and Cu/TiO2 catalysts. In addition, apparent activation energies of 12 and 19.5 kJ/mol found with Pt/TiO2 and Cu/TiO2 catalysts respectively indicate diffusion limitations which favor back oxidation reactions resulting in low reduction yields. Photocatalytic CO2 reduction reaction is named as Artificial Photosynthesis even though present artificial system does not have sophisticated transport and membrane systems which natural systems have. Similarities and differences between artificial and natural photosynthesis are studied in order to present ideas to improve present photocatalytic rates. Kinetic and microkinetic modeling of catalytic methanol production from CO2 hydrogenation on Cu surfaces were performed in order to have an idea about kinetic limitations at photocatalytic systems. Calculations were performed at temperatures and pressures at which photocatalytic studies are conducted. The results indicated that water has an inhibitory effect on methanol formation rates and higher pressures could be implemented in photocatalytic systems for higher rates. Another implication drawn from degree of rate control calculations is that H formation step plays an important role underlying the importance of water splitting in CO2 reduction reactions.

High rate algal ponds (HRAPs) are an advanced pond that provide efficient and cost-effective wastewater treatment, as well as the ability to recover nutrients in the form of microalgal biomass. Microalgal photosynthesis, nutrient uptake and subsequent growth, coupled with aerobic bacteria degradation of organic compounds, are fundamental to the process of wastewater treatment in HRAPs, yet are often limited in these ponds and, in particular, microalgal photosynthesis is well below the reported theoretical maximum. Understanding how the physico-chemical environment affects microalgal performance is therefore critical to improved wastewater treatment and nutrient recovery, yet has been the subject to few studies to date. This research focused on the enhancement of microalgal photo-physiology, growth and nutrient removal efficiency (NRE) through modification to the physical and chemical environment in wastewater HRAPs. In this study, I first examined the seasonal dynamics of microalgal performance in full-scale wastewater HRAPs. While both retention-time corrected chlorophyll biomass and photosynthetic potential increased from winter to summer, the summer-time performance was considered to be constrained, as indicated by the decreased light absorption, light conversion efficiency and NRE. The physico-chemical environment in the full-scale HRAPs were characterised by high day-time pH, high light attenuation and long, straight channels with low turbulence. This led to questions regarding 1) effects of nutrient supply, in particular carbon and 2) the role of the HRAP light climate on microalgal performance. I addressed these questions using a series of experiments that involved either changing the nutrient concentration and its supply or by modifying the light environment, through changes in pond operational parameters including CO2 addition, influent dilution, pond depth, hydraulic retention time (HRT), mixing speed and frequency. The overall results from these experiments showed that carbon was the primary and light the secondary limiting factors of microalgal performance. These limitations negatively affected light absorption, photosynthesis, productivity and NRE. While each operational parameter tested impacted on microalgal performance, to some degree, CO2 addition had the greatest influence on light absorption, photosynthetic efficiency and productivity, while continuous mixing had the greatest effect on NRE. Adding CO2 increased light absorption by 110% and 128%, maximum rate of photosynthesis by 185% and 218% and microalgal biovolume by between 150 – 256% and 260 – 660% (species specific), when cultures were maintained at pH 8 and 6.5, respectively. Providing sufficient mixing to achieve continuous turbulence enhanced NRE by between 300 – 425% (species specific), increased biomass concentrations between 150% and 4000% (species specific) compared to intermittent and no mixing, respectively, and increased harvest-ability of colonial species. However, at present, both CO2 addition and mechanical mixing attract high capital and operational costs. Modification to these technologies would be required to meet the objectives of cost-effective wastewater treatment and biofuel production. A more immediate and cost-effective solution demonstrated in this study was the altering pond depth, influent concentration and HRT. Doubling pond depth from 200 to 400 mm increased both microalgal nutrient removal and photosynthetic efficiencies which led to areal productivity increasing by up to 200%. When increased pond depth was coupled with decreased HRT, light absorption and photosynthetic performance further increased due to decreased internal self-shading and improved pond light climate. For nutrients, high influent loads increased productivity, while moderate loads increased effluent water quality. Overall, this work demonstrated that optimising the chemical and physical environment of wastewater treatment HRAPs (CO2 addition to maintain pH at 6.5 – 7, 400 mm pond depth, continuous mixing with vertical speed of 200 mm s-1, moderate nutrient load (15- 30 g m-3) and moderate HRT (4 / 6 days summer / autumn) can enhance microalgal biomass productivity, nutrient recovery as well as improve effluent water quality, particularly during summer when growth can be constrained.

This study examines the evolutionary history of Pectis L., a neotropical genus of ~90 species of xeric-adapted, herbaceous, annuals and perennials. Pectis is rare among the Asteraceae, as it uses C₄ photosynthesis, a complex suite of traits that concentrates carbon around Rubisco. Plants with C₄ photosynthesis do well in environments of high light and high heat, and the C₄ syndrome is thought to have evolved as a response to such environments. Pectis is most diverse in Mexico, the Caribbean Islands, and South America, and its distribution mirrors the disjunctions of patches of desert, thornscrub, coastal plains, savanna, and openings in seasonally-dry tropical forests and oak-pine woodlands. Vicariance and long-distance dispersal theories can explain the patchy distribution of xeric-adapted plants, as well as the origin of Caribbean species. To answer evolutionary questions about a group, one must understand how its members are related. The most comprehensive taxonomic treatment of Pectis is over 100 years old, and includes only North American species. Recent revisions still leave half the species unassigned to section. Molecular studies have found Pectis sister to, or encompassing, the genus Porophyllum. To infer evolutionary relationships between and within Pectis and Porophyllum, DNA from the nuclear and chloroplast genomes of 78 Pectis and 22 Porophyllum species were sampled, sequenced, and analyzed. The molecular phylogeny was used to suggest updated sections based on monophyletic groups. To infer the photosynthetic pathway of Pectis and Porophyllum species, carbon isotope ratios were obtained from 62 Pectis and 18 Porophyllum species. The timing and location of the evolution of Pectis and Porophyllum has implications for the evolution of C₄ photosynthesis. The carbon isotope data were combined with the phylogeny to determine the extent and direction of the evolution of C₄ photosynthesis, and the timing of its evolution was inferred from a fossil-calibrated analysis using chloroplast data from species across the Asteraceae. Distribution data was combined with the Pectis phylogeny to answer questions regarding the biogeographical history of Pectis, including questions regarding its disjuncted distribution, the timing of the evolution of desert species, and the timing and pattern of dispersal to and from the Caribbean Islands. / text

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Plants, green algae and cyanobacteria perform photosynthetic conversion of sunlight into chemical energy in the permanently changing natural environment. For successful survival and growth photosynthetic organisms have developed complex sensing and signaling acclimation mechanisms. The environmentally dependent protein phosphorylation in photosynthetic membranes is implied in the adaptive responses; however, the molecular mechanisms of this regulation are still largely unknown. We used a mass spectrometry-based approach to achieve a comprehensive mapping of the in vivo protein phosphorylation sites within photosynthetic membranes from the green alga Chlamydomonas reinhardtii subjected to distinct environmental conditions known to affect the photosynthetic machinery. The state transitions process regulating the energy distribution between two photosystems, involves the temporal functional coupling of phosphorylated light-harvesting complexes II (LHCII) to photosystem I (PSI). During state transitions several of the thylakoid proteins undergo redox-controlled phosphorylation-dephosphorylation cycles. This work provided evidences suggesting that redox-dependent phosphorylation-induced structural changes of the minor LHCII antenna protein CP29 determine the affinity of LHCII for either of the two photosystems. In state 1 the doubly phosphorylated CP29 acts as a linker between the photosystem II (PSII) core and the trimeric LHCII whereas in state 2 this quadruply phosphorylated CP29 would migrate to PSI on the PsaH side and provide the docking of LHCII trimers to the PSI complex. Moreover, this study revealed that exposure of Chlamydomonas cells to high light stress caused hyperphosphorylation of CP29 at seven distinct residues and suggested that high light-induced hyperphosphorylation of CP29 may uncouple this protein together with LHCII from both photosystems to minimize the damaging effects of excess light. Reversible phosphorylation of the PSII reaction center proteins was shown to be essential for the maintenance of active PSII under high light stress. Particularly dephosphorylation of the light-damaged D1 protein, a central functional subunit of the PSII reaction center, is required for its degradation and replacement. We found in the alga the reversible D1 protein phosphorylation, which until our work, has been considered as plant-specific. We also discovered specific induction of thylakoid protein phosphorylation during adaptation of alga to limiting environmental CO2. One of the phosphorylated proteins has five phosphorylation sites at both serine and treonine residues. The discovered specific low-CO2- and redox-dependent protein phosphorylation may be an early adaptive and signalling response of the green alga to limitation in inorganic carbon. This work provides the first comprehensive insight into the network of environmentally regulated protein phosphorylation in algal photosynthetic membranes.