Harvesting solar energy can potentially be a promising solution to the energy crisis now and in the future. However, material and processing costs continue to be the most important limitations for the commercial devices. A key solution to these problems might lie within the development of bio-hybrid solar cells that seeks to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. The bio-photoelectrochemical cell technologies exploit biomimetic means of energy conversion by utilizing plant-derived photosystems which can be inexpensive and ultimately the most sustainable alternative. Plants and photosynthetic bacteria harvest light, through special proteins called reaction centers (RCs), with high efficiency and convert it into electrochemical energy. In theory, photosynthetic RCs can be used in a device to harvest solar energy and generate 1.1 V open circuit voltage and ~1 mA cm-2 short circuit photocurrent. Considering the nearly perfect quantum yield of photo-induced charge separation, efficiency of a protein-based solar cell might exceed 20%. In practice, the efficiency of fabricated devices has been limited mainly due to the challenges in the electron transfer between the protein complex and the device electrodes as well as limited light absorption. The overarching goal of this work is to increase the power conversion efficiency in protein-based solar cells by addressing those issues (i.e. electron transfer and light absorption). This work presents several approaches to increase the charge transfer rate between the photosynthetic RC and underlying electrode as well as increasing the light absorption to eventually enhance the external quantum efficiency (EQE) of bio-hybrid solar cells. The first approach is to decrease the electron transfer distance between one of the redox active sites in the RC and the underlying electrode by direct attachment of the of protein complex onto Au electrodes via surface exposed cysteine residues. This resulted in photocurrent densities as large as ~600 nA cm-2 while still the incident photon to generated electron quantum efficiency was as low as %3 × 10-4. 2- The second approach is to immobilize wild type RCs of Rhodobacter sphaeroides on the surface of a Au underlying electrode using self-assembled monolayers of carboxylic acid terminated oligomers and cytochrome c charge mediating layers, with a preferential orientation from the primary electron donor site. This approach resulted in EQE of up to 0.06%, which showed 200 times efficiency improvement comparing to the first approach. In the third approach, instead of isolated protein complexes, RCs plus light harvesting (LH) complexes were employed for a better photon absorption. Direct attachment of RC-LH1 complexes on Au working electrodes, resulted in 0.21% EQE which showed 3.5 times efficiency improvement over the second approach (700 times higher than the first approach). The main impact of this work is the harnessing of biological RCs for efficient energy harvesting in man-made structures. Specifically, the results in this work will advance the application of RCs in devices for energy harvesting and will enable a better understanding of bio and nanomaterial interfaces, thereby advancing the application of biological materials in electronic devices. At the end, this work offers general guidelines that can serve to improve the performance of bio-hybrid solar cells.

Magister Scientiae (Biodiversity and Conservation Biology) / Elevated temperatures accompanying climate warming are expected to have adverse effects on sensitive lichen species. This premise was examined by measuring the sensitivity of different lichen species to elevated temperatures in the laboratory and in the field. Laboratory studies involved the exposure of nine hydrated lichen species (Xanthoparmelia austro-africana, X. hyporhytida, Xanthoparmelia sp., Xanthomaculina hottentotta, Teloschistes capensis, Ramalina sp., Flavopuntelia caperata, Lasallia papulosa, Parmotrema austrosinensis) collected from sites of different aridity and mean annual temperature for 2 hourly intervals to temperatures ranging from 24ºC to 48ºC in a forced daft oven and measuring their respiration rates and maximum quantum yield of PSII. Field studies involved simultaneous hourly measurements of ground surface air temperatures and Lichen effective quantum yield of PSII of hydrated lichen species populations under ambient and artificially modified environmental conditions. / South Africa

Eddy-covariance (EC) CO₂ flux data were analysed and annual carbon (C) balances estimated for a four-year period (2004-2007) following clearcut harvesting of a boreal jack pine stand in northern Saskatchewan. The site was a source of C to the atmosphere for all years, with annual net ecosystem productivity (NEP) increasing from -153 g C m⁻² yr⁻¹ in 2004 to -63 g C m⁻² yr⁻¹ in 2007. This increase was mainly due to gross primary productivity (GPP) increasing significantly from 78 to 200 g C m⁻² yr⁻¹ , while ecosystem respiration (R) increased only slightly from 231 to 263 g C m⁻² yr⁻¹ over the same period. In the 2006 growing season (GS), a field campaign was conducted to investigate the relationships between monthly destructive measurements of leaf area index (LAI) and daily measurements of the normalized difference vegetation index (NDVI) and photosynthetic capacity (Amax). The latter was derived from 5-day, 16-day, 30-day and annual Michaelis-Menten light response analyses using daytime measurements of NEP and incident photosynthetically active radiation. Digital-camera data were used to evaluate the potential of using the rectilinear-lens vegetation index (RLVI) as a surrogate for NDVI of a young forest stand. Results showed that LAI was linearly related to NDVI and RLVI, which was largely the result of changes in the deciduous vegetation component across the GS. These results indicate that RLVI could be used as a surrogate for NDVI up to a GS maximum LAI of 0.91 m2 m⁻² observed in 2006. Measured mean (± 1 S.D.) GS LAI was 0.67 (± 0.24) m² m⁻² in 2006. LAI accounted for the majority of the variability in Amax at the 30-day time scale, while at shorter time scales air temperature was the dominant control. For 2004 to 2007, mean spring estimates of LAI were 0.25, 0.29, 0.38 (compared to 0.40 m² m⁻² from measurements) and 0.41 m² m⁻², respectively. Results suggest that a steady increase in the jack pine LAI component accounted for the annual increases in GPP and hence NEP over the four years. / Land and Food Systems, Faculty of / Graduate

>Magister Scientiae - MSc / Antarctica is known for its pristine environments. A variety of unsuitable environmental conditions were once thought to render the continent unsuitable for sustaining life. However, metagenomic data have revealed a wealth of species diversity in a range of biotopes.Hypolithons, photosynthetic communities which live under translucent rocks in climatically extreme environments, are an important input source for both carbon (C) and nitrogen (N) in this hyperarid desert environment. Microbial contribution to biogeochemical cycling resulting in fixation of both C and N remains poorly understood. Moreover, there is a reported close interplay between both cycles, with nitrogen being reported to be a limiting factor in carbon assimilation.In this study the diversity of C and N fixing organisms was investigated by using the cbbL and nifH genes as phylogenetic and functional markers. High Molecular weight metagenomic DNA and RNA was extracted from hypolithons. PCR amplification was carried out using cbbL (800 bp for red-like, 1,100 bp for green-like) and nifH (360 bp) gene specific primers.Resultant PCR products were used to construct libraries which were screened for correct sized inserts. Restriction Fragment Length Polymorphism (RFLP) was used to de-replicate clones prior to sequencing. Phylogenetic positions from both clone libraries were established by aligning nucleotide sequences and constructing similarity trees using NJ clustering methods.BLASTn results indicated the presence of previously uncultured organisms which contain cbbL and nifH genes. BLASTn results were characterized by low percentages of maximum identity (typically <95%), a potential indicator of novel taxa. Sequences from respective libraries clustered with cyanobacteria such as Nostoc, Scytonema, and Tolypothrix and α-, β-, and γ-Proteobacteria such as Azotobacter, Agrobacterium and Mesorhizobium. Generally sequence results indicate a largely homogenous, being dominated by specific taxa. Each group may contain potential keystone species, essential for both biogeochemical cycling in oligotrophic environment.

O estresse de luz pode afetar consideravelmente o crescimento e o desenvolvimento dos organismos fotossintetizantes. Nestas situações, é comum verificar respostas químicas que podem indicar diferentes estratégias de fotoproteção adotado pelo organismo. No presente trabalho, foram desenvolvidas metodologias de análise e extração de pigmentos fotossintetizantes e compostos fenólicos na macroalga vermelha Gracilariopsis tenuifrons com o objetivo de avaliar os efeitos do aumento intensidade de luz sobre estes compostos. Foi verificado que aumento da intensidade de luz não provocou redução na biomassa desta alga, ao contrário houve um maior incremento. Os pigmentos majoritários no extrato foram clorofila &alpha;, &beta;-caroteno e zeaxantina. O carotenoide &beta;-caroteno teve um comportamento correlacionado com o pigmento clorofila a, tendo as concentrações reduzidas com o aumento da intensidade de luz, sugerindo que ambos os pigmentos possuam uma mesma função na fotossíntese. Já a concentração da zeaxantina aumentou com a intensidade de luz nos dias iniciais, indicando uma função fotoproteção deste pigmento nesta alga. A capacidade redutora do extrato aumentou com a intensidade luminosa. No entanto, não foi possível afirmar se esse aumento foi realmente devido à síntese de compostos fenólicos ou a outras substâncias que desempenhem o mesmo papel. As análises em CLAE revelaram que um derivado da micosporina palitinol apresentou alta relação com o aumento da intensidade de luz, sendo essa resposta altamente correlacionada com os resultados no ensaio no Folin-Ciocalteu. Em conclusão, das substâncias analisadas neste trabalho, a zeaxantina e o derivado do palitinol foram as que apresentaram os resultados mais evidentes como antioxidantes / The high-light stress can adversely affect growth and development of photosyn-thetic organisms. In these situations, it is common to note chemical responses that may indicate different strategies of photoprotection. In this study, protocols were optimized for analysis and extraction of phenolic compounds and photosynthetic pig-ments in macrophytic red algae Gracilariopsis tenuifrons in order of evaluat-ing the effects of high-light stress on these compounds. It was found that an increase in light intensity has not caused decrease in biomass of algae; on the contrary, promotes a greater increase in biomass. Zeaxanthin, &beta;-carotene and chlorophyll &alpha; were the major pigments present in the extract. The &beta;-carotene and chlorophyll a were inversely dependent on the intensity of light. Both pigments were highly correlated sug-gesting the same role in photosynthesis. The concentration of the zeaxanthin was de-pendent on the intensity of light in the initial days, indicating a photoprotection function for this pigment. The reduction capacity of the extract increased with light intensity. However, it was not possible to state that this increase was actually due to the synthesis of phenolic compounds or other substances that perform the same role. The HPLC ana-lyzes revealed that a derivative of micosporina palitinol showed high correlation with the increase in light intensity. This response was highly correlated with the results for Folin-Ciocalteu assay. In conclusion, from all compounds analyzed in this work, zeax-anthin and the palitinol derivative presented clearer results as antioxidants

Ce travail de thèse porte sur l’effet du rayonnement UV-B sur la physiologie foliaire et la maturation des baies chez la Vigne (Vitis vinifera L. cv Tempranillo), dans le contexte du changement climatique en cours. Dans ce but, des expériences ont été menées en conditions contrôlées en serre, sur des boutures fructifères. Les plantes ont été exposées à trois doses de rayonnement UV-B biologiquement actifs (0, 5,98 et 9,66 kJ.m-2.jour-1), soit à partir de la nouaison, soit à partir de la véraison, et ce jusqu’à la pleine maturité. Le rayonnement UV-B a été appliqué seul ou en combinaison avec d’autres stress abiotiques (déficit hydrique, taux de CO2 et température élevés). L’impact de ces stress sur l’activité photosynthétique, les contenus en pigments et en composés photoprotecteurs, ainsi que sur les activités des enzymes produisant des composés antioxydants, ont été étudiés. La phénologie, les profils d’accumulation des flavonols et des anthocyanes, ainsi que le contenu en acides aminés des baies ont également été analysés, de même que l’expression des principaux gènes régulateurs et structuraux de la voie de biosynthèse des polyphénols. Les résultats obtenus montrent que les effets des UV-B sur la physiologie foliaire peuvent être découpés en deux phases : une première phase transitoire de diminution de l’activité photosynthétique, suivie d’une phase d’acclimatation due à la production de composés photoprotecteurs (flavonoïdes essentiellement) et à l’activité d’enzyme de détoxification des forme actives de l’oxygène (superoxyde dimutase, catalase, ascorbate peroxidase). Le déficit hydrique, le stress thermique et un taux de CO2 élevé (700ppm, +4ºC) ne modifient pas le processus d’acclimatation aux UV-B ; en revanche on note une interaction positive entre les UV-B d’une part et la tolérance aux températures et au taux de CO2 élevé d’autre part, atténuant les dommages oxydatifs dus à l’induction de sénescence par ces deux derniers facteurs. La maturité des baies est retardée par les UV-B et le déficit hydrique, et ce phénomène et amplifiés lorsque ces deux stress sont appliqués en combinaison ; alors que les hautes températures et un taux de CO2 élevé ont l’effet inverse. Dans ce dernier cas, le UV-B rayonnement atténue les effets du couple température/CO2 élevés. Ces effets sur la phénologie de la Vigne ont pu être reliés à des modifications de l’activité photosynthétique des feuilles. En ce qui concerne la composition des baies, l’augmentation du rayonnement UV-B et le déficit hydrique ont augmenté les concentrations en anthocyanes et en potassium des moûts et diminué leur acidité, ce qui peut s’expliquer en partie par une augmentation du ratio de masse pellicule/pulpe. L’augmentation des teneurs en anthocyanes et flavonols des pellicules observée en réponse aux UV-B a pu être reliée à l’induction de gènes structuraux (CHS, F3’H, FLS, UFGT and GST) et régulateurs (MYBF1 et MYBA1) de la voie de biosynthèse des flavonoïdes. Ces changements quantitatifs étaient toujours associés à des changements qualitatifs, avec une augmentation de la part relative des flavonols mono- et disubstitués, en raison d’une compétition de la flavonol synthase avec les F3’ et F3’5’ hydroxylases pour les mêmes substrats. Une interaction notable a été observée entre le rayonnement UV-B et le déficit hydrique, sur les profils d’hydroxylation des flavonols, ce qui s’explique par le fait que ces deux facteurs agissent sur deux étapes distinctes de la voie de biosynthèse. / The aim of the thesis was to assess the effect of UV-B radiation on grapevine Vitis viniferacv. Tempranillo leaf physiology and grape berry composition, framed within the climatechange scenario. Experiments were conducted under glasshouse controlled conditions withfruit-bearing cuttings. Plants were exposed to three UV-B biologically effective doses (0,5.98, 9.66 kJ m-2 d-1) either from fruit set or veraison to maturity. The combined effects of UVand water deficit, as well as, UV-B and elevated CO2-temperature (700ppm, +4ºC), appliedfrom fruit set to maturity were also tested. Gas exchange, Chlorophyll a fluorescence, lipidperoxidation, antioxidant enzyme activity, UV-B absorbing compound levels and chlorophylland carotenoid concentration were determined in leaves. Berry development was assessedquantitatively (e.g. elapsed time to reach phenological stages). Amino acid, anthocyanin andflavonol concentrations and profiles were analyzed in berries, as well as, transcript profilingof regulatory and structural genes involved in flavonoid biosynthesis.The results show that initial down-regulation of photosynthesis was followed by anacclimation, mediated by the accumulation of UV-B absorbing compounds and antioxidantresponse elicitation (flavonoids and antioxidant enzymes). Water deficit and elevated CO2-temperature did not alter UV-B acclimation process, however, UV-B did led to certain degreeof cross-tolerance to elevated CO2-temperature, avoiding the senescence-induced oxidativedamage. Berry technological maturity (ca. 22ºBrix) was delayed by UV-B exposure and waterdeficit, especially when combined, whereas it was hastened by elevated CO2-temperature. Inthe last case, UV-B attenuated the effect of elevated CO2 and temperature. Changes in berryripening rates were associated with changes in photosynthetic performance.UV-B radiation and water deficit induced lower grape must acidity, mediated by increases inrelative skin mass or potassium levels rather than a decrease in organic acid concentration.In addition this increase in relative skin mass may have contributed to higher anthocyaninconcentration in the must. Grape berry skin flavonol and anthocyanin concentration wasincreased by UV-B, mainly due to the up-regulation of the structural (CHS, F3’H, FLS, UFGTand GST) and regulatory genes (MYBF1 and MYBA1) committed to their synthesis.Quantitative changes in flavonol concentration induced by UV-B were always associated withqualitative changes in flavonol profile (i.e. increased relative abundance of mono- anddisubstituted flavonols), as a result of the competition of FLS with flavonoid hydroxylases(F3’H and F3’5’H) for the same substrates. The independent up-regulation of FLS and F3’5’Hby UV-B radiation and water deficit, respectively, resulted in an intaractive effect on theflavonol B ring hydroxylation pattern. Under elevated CO2-temperature anthocyanin-sugaraccumulation was decoupled. However, UV-B partially alleviated this uncoupling by upregulatinganthocyanin biosynthesis and modulating berry ripening rates.UV-B radiation greatly influenced grapevine leaf physiology and berry composition. Theseresponses to UV-B were modulated, to a greater or lesser extent, by other factors linked toclimate change (water availability, atmospheric CO2 levels and temperature).

Nanoparticles are particles with sizes between 1 and 100 nanometers (nm). Owing to their unique chemical, electrical, mechanical, optical, and piezoelectric properties, zinc oxide nanoparticles (ZnO-NPs) are finding widespread use in numerous applications with yearly production over 550 tons per year. Increasing use of ZnO NPs, and NPs in wastewater discharges from domestic and industrial sources will have significant potential for adverse impacts on aquatic phototrophic organisms. Comparative studies on microalgae species response to ZnO NPs and variation in tolerance among species is still mostly unexplored. The proposed research aims to evaluate interspecies’ variation in tolerance to ZnO NPs among marine and freshwater microalgae. Multi-well culture plate and flask culture screening methods were utilized for assessing microalgae species’ tolerance to various levels of ZnO NPs. Microalgae cell morphology changes in response to nano ZnO exposure were explored using both the Optical Coherence Microscope (OCM) and SEM. Availability of Nano ZnO tolerant microalgae species may provide an impetus for future studies to understand the mechanism of tolerance and potential applications in NPs bioremediation in aquatic systems.

Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Tracing the evolution of Earth's redox history is one of the great challenges of geobiology and geochemistry. The accumulation of photosynthetically derived oxygen transformed the redox state of Earth's surface environments, setting the stage for the subsequent evolution of complex life. However, the timing of the advent of oxygenic photosynthesis relative to the Great Oxidation Event (GOE; -2.4 Ga) is poorly constrained. After the deep ocean became oxygenated in the early Phanerozoic, hydrogen sulfide, which is toxic to most aerobes, may have transiently accumulated in the marine photic zone (i.e. photic zone euxinia; PZE) during mass extinctions and oceanic anoxic events. Here, the molecular fossil evidence for oxygenic photosynthesis and eukaryotes is reevaluated, where the results imply that currently existing lipid biomarkers are contaminants. Next, the stratigraphic distribution of green and purple sulfur bacteria biomarkers through geologic time is evaluated to test whether these compounds reflect a water column sulfide signal, which is implicit in their utility as PZE paleoredox proxies. Results from a modern case study underscore the need to consider allochthonous and microbial mat sources and the role of basin restriction as alternative explanations for these biomarkers in the geologic record, in addition to an autochthonous planktonic source. / by Katherine L. French. / Ph. D.

No description available.

La recherche de sources d’énergie fiables ayant un faible coût environnemental est en plein essor. L’hydrogène, étant un transporteur d’énergie propre et simple, pourrait servir comme moyen de transport de l’énergie de l’avenir. Une solution idéale pour les besoins énergétiques implique une production renouvelable de l’hydrogène. Parmi les possibilités pour un tel processus, la production biologique de l’hydrogène, aussi appelée biohydrogène, est une excellente alternative. L’hydrogène est le produit de plusieurs voies métaboliques bactériennes mais le rendement de la conversion de substrat en hydrogène est généralement faible, empêchant ainsi le développement d’un processus pratique de production d’hydrogène. Par exemple, lorsque l’hydrogène est produit par la nitrogénase sous des conditions de photofermentation, chaque molécule d’hydrogène constituée requiert 4 ATP, ce qui rend le processus inefficace. Les bactéries photosynthétiques non sulfureuses ont la capacité de croître sous différentes conditions. Selon des études génomiques, Rhodospirillum rubrum et Rhodopseudomonas palustris possèdent une hydrogénase FeFe qui leur permettrait de produire de l’hydrogène par fermentation anaérobie de manière très efficace. Il existe cependant très peu d’information sur la régulation de la synthèse de cette hydrogénase ainsi que sur les voies de fermentation dont elle fait partie. Une surexpression de cette enzyme permettrait potentiellement d’améliorer le rendement de production d’hydrogène. Cette étude vise à en apprendre davantage sur cette enzyme en tentant la surexpression de cette dernière dans les conditions favorisant la production d’hydrogène. L’utilisation de résidus organiques comme substrat pour la production d’hydrogène sera aussi étudiée. / The search for alternative energy sources with low environmental impact is in great expansion. Hydrogen, an elegant and simple energy transporter, could serve as means of transporting energy in the future. An ideal solution to the increasing energy needs would imply a renewable production of hydrogen. Out of all the existing possibilities for such a process, the biological production of hydrogen, also called biohydrogen, is an excellent alternative. Hydrogen is the end result or co-product of many pathways in bacterial metabolism. However, such pathways usually show low yields of substrate to hydrogen conversion, which prevents the development of efficient production processes. For example, when hydrogen is produced via nitrogenase under photofermentation conditions, each hydrogen molecule produced requires 4 molecules of ATP, rendering the process very energetically inefficient. Purple non-sulfur bacteria are highly adaptive organisms that can grow under various conditions. According to recent genomic analyses, Rhodospirillum rubrum and Rhodopseudomonas palustris possess, within their genome, an FeFe hydrogenase that would allow them to produce hydrogen via dark fermentation quite efficiently. Unfortunately, very little information is known on the regulation of the synthesis of this enzyme or the various pathways that require it. An overexpression of this hydrogenase could potentially increase the yields of substrate to hydrogen conversion. This study aims to increase our knowledge about this FeFe hydrogenase by overexpressing it in conditions that facilitate the production of hydrogen. The use of organic waste as substrate for hydrogen production will also be studied.