Wheat canopies were grown at either 330 or 1200 μmol mol-1 CO2 in sealed controlled environments, where carbon fluxes and radiation interception were continuously and nondestructively measured during their life cycles. The effects of elevated CO2 on daily growth rates, canopy quantum yield, canopy and root carbon use efficiencies, and final dry mass were calculated from carbon flux measurements in an open gas exchange system. Dry biomass at harvest was predicted from the gas exchange data to within ± 8%. The greatest effect of elevated CO2 occurred in the first 15d after emergence; however, several physiological processes were enhanced throughout the life cycle. Elevated CO2 increased average net photosynthesis by 30%, average shoot respiration by 10%, and average root respiration by 40%. Crop growth rate, calculated from gas exchange data, was 30% higher during both vegetative growth and reproductive growth. Elevated CO 2 did not affect radiation interception, but increased average canopy quantum yield from 0.039 to 0.051 (31%). Average canopy carbon use efficiency was increased by 12%. Although harvest index was unaffected, these increases in the physiological determinants of yield by elevated CO2 resulted in a 14% increase in seed yield.

<p>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 24&ordm / C to 48&ordm / C 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.</p>

<p>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 24&ordm / C to 48&ordm / C 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.</p>

Made available in DSpace on 2016-06-02T19:32:09Z (GMT). No. of bitstreams: 1 5910.pdf: 1437016 bytes, checksum: 8d574c7743c2d70359b23e9e449a0b53 (MD5) Previous issue date: 2014-06-16 / Financiadora de Estudos e Projetos / Phytoplankton cells are base of aquatic food webs, so supporting higher trophic levels and helping equilibrium maintenance in such ecosystems. As residues, nano-TiO2 particles reach aquatic environments where they pose risks to the biota. Literature is controversial about the toxicity of nanoparticles to phytoplankton in general and most data obtained so far has been based on nanoparticles concentrations well above those estimated to occur in natural aquatic environments. Because nanoparticles size vary according to its concentrations, and its toxicity and reactivity are largely dependent on its size, investigations of nanoparticles toxicity at environmentally relevant concentrations are important for the understanding of these compounds onto phytoplankton cells. On the contrary, investigations using higher concentrations can be meaningless. This study aimed at investigating the effects of titanium dioxide nanoparticles (nano-TiO2) at environmentally relevant concentrations (5.10-9 to 5.10- 6 mol L-1) on the freshwater Chlorophyceae Scenedesmus bijugus. We present data of a systematic investigation onto the effects of TiO2 nanoparticles to Scenedesmus bijugus focusing on its physiology under controlled laboratory conditions. We evaluated cell density, chlorophyll a concentrations, growth rates, photosynthetic quantum yield of PSII (continue...) / Células do fitoplâncton são a base de cadeias alimentares aquáticas, apoiando níveis tróficos superiores e ajudando na manutenção do equilíbrio desses ecossistemas. Na qualidade de resíduos, as nano-TiO2 alcançam os ambientes aquáticos onde podem impor riscos à biota. A literatura é controversa sobre a toxicidade de nanopartículas ao fitoplâncton e, em geral, a maioria dos dados têm sido obtidos com base em concentrações de nanopartículas superiores às estimadas para ambientes aquáticos naturais. Considerando que as nanopartículas variam de tamanho de acordo com sua concentração, em decorrência da formação de agregados e, que sua toxicidade e reatividade são dependentes de seu tamanho, investigações sobre a toxicidade desses materiais devem ser feitas empregando-se concentrações ambientalmente importantes, ou seja, aquelas que podem ser encontradas em ecossistemas naturais. Este estudo teve como objetivo investigar os efeitos das nanopartículas de dióxido de titânio (nano-TiO2) na clorofícea de água doce Scenedesmus bijugus em concentrações ambientalmente representativas. Nesta pesquisa, apresentamos dados de uma investigação sistemática sobre os efeitos de nano-TiO2 em amplitude de concentração de 5.10-9 a 5.10-6 mol L-1 em Scenedesmus bijugus, focando em sua fisiologia sob condições controladas de laboratório. Foram avaliadas a densidade de células, as concentrações de clorofila a, taxas de crescimento, rendimento quântico máximo do PSII (continua...)

Orientador: Luiz Fernando Rolim Almeida / Resumo: Espera-se que os efeitos da seca aumentem e alterem a duração do estresse hídrico nos próximos anos em diferentes regiões agrícolas. A recuperação fisiológica após o estresse hídrico ainda não é compreendida e as aquaporinas (AQPs) participam do processo de recuperação. Nosso objetivo foi avaliar se as aquaporinas estão associadas com o processo de recuperação fisiológica nas folhas após a reidratação. Plantas de Sorghum bicolor L. (Moench) foram submetidas a diferentes intensidades de estresse hídrico durante 20 dias e posterior reidratação durante 12 dias. Durante estes períodos, as variáveis de relações hídricas, fluorescência da clorofila a, trocas gasosas e a expressão dos genes PIP1,5, PIP2;2 e TIP1; 1 foram avaliados. Plantas submetidas ao déficit hídrico moderado (DHM) mostraram mesmos valores do controle em todas as variáveis fisiológicas e aumento da expressão das aquaporinas no final do déficit hídrico. Enquanto as plantas da deficiência hídrica severa (DHS) e severa progressiva (DHSP) apresentaram diminuição nas variáveis de relações hídricas, limitação estomática e não estomática da fotossíntese e baixa expressão das aquaporinas. Após a reidratação, as plantas desses tratamentos apresentam conjunto de ajustes fisiológicos que permitem o retorno da fotossíntese 144 horas após o fornecimento de água, sendo a limitação estomática a maior responsável pela recuperação. As AQPs analisadas são responsivas à reidratação somente nas plantas que não tiveram controle da rep... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: It is expected that the effects of drought increase and change the duration of water stress in the coming years in different agricultural regions. The physiological recovery after water stress is still not well understood and aquaporins (AQPs) participate in the recovery process. Our aim was evaluate whether aquaporins are associated with physiological recovery process in leaves after rehydration. Sorghum bicolor L. (Moench) plants were submitted to different intensities of water stress during 20 days and subsequent rehydration for 12 days. During these periods, variables of water relations, chlorophyll fluorescence, gas exchange and PIP1;5, PIP2;2 and TIP1;1 gene expression were evaluated. Moderate water deficit (DHM) plants showed same values of control in all physiological variables and increased aquaporins expression in the end of water deficit. While severe (DHS) and progressive severe water stress (DHSP) plants had decreased water relations, diffusive and non-diffusive limitation of photosynthesis and low aquaporins expression. After rehydration, plants of these treatments have set of physiological adjustments that enable the return of photosynthesis 144 hours after the water supply. Stomatal limitation was the most responsible for recovery. The AQPs analyzed are responsive to rehydration only in plants that did not have control of water replacement in the soil (DHSP). We observed a pattern of responses of these AQPs that depends on the intensity of water deficit and no... (Complete abstract click electronic access below) / Mestre

Neste trabalho, estudou-se a degradação do bisfenol A (BPA) em solução aquosa através da fotólise direta sob radiação UV em 254 nm. Os experimentos foram realizados um reator fotoquímico tubular de vidro de 3,9 L, equipado com uma lâmpada de vapor de mercúrio de baixa pressão tubular concêntrica (36 W). Avaliaram-se os efeitos da taxa específica de emissão de fótons (0,87×10 18 ; 1,4×1018 e 3,6×1018 fótons L-1 s-1 ) e da concentração inicial de BPA (10 a 50 mg L-1 ), conforme um projeto experimental Doehlert. Os resultados dos experimentos indicaram que a degradação do BPA diminui com o aumento de sua concentração inicial, seguindo decaimento de pseudo primeira-ordem. A constante cinética de velocidade de degradação do BPA variou de 0,001 a 0,0066 min-1 , enquanto a porcentagem de degradação de BPA ao final de 120 minutos variou de 14 a 55%; já a remoção do carbono orgânico total variou entre 1,5 e 12,5%. Houve a formação de produtos persistentes e as espécies reativas de oxigênio (1 O2 oOH ) mostraram-se muito importantes durante a degradação do BPA. O rendimento quântico para fotólise de BPA foi de 0,0075 mol BPA mol fótons-1, determinado a partir dos dados experimentais através de um modelo matemático para degradação fotolítica do BPA em função do tempo. Para tanto, considerou-se um sistema de tratamento formado por um reator tubular e um tanque de mistura com recirculação entre eles, sendo o reator tubular tratado como uma série de três reatores contínuos de mistura perfeita (CSTR) associados entre si. Através da análise estatística dos dados experimentais para duas respostas (constante específica de degradação do BPA e porcentagem de degradação do BPA ao final de 120 minutos) avaliaram-se os efeitos das variáveis envolvidas (concentração inicial de BPA e taxa específica de emissão de fótons). / The aim of this study was to evaluate bisphenol A (BPA) degradation in aqueous solution by direct photolysis under UV radiation at 254 nm, considering the effects of the specific rate of photon emission (0.87×1018; 1.4×1018 and 3.6×1018 fótons L-1 s-1) and the initial BPA concentration (10-50 mg L-1), according to a Doehlert experimental design. The experiments were performed in a glass tubular photochemical reactor of 3.9 L equipped with a concentric low pressure mercury vapor lamp of 36 W. The experimental results indicated that BPA degradation decreases with increasing initial concentration, following pseudo first-order decay, and increases with increasing specific rate of photon emission. The values of the specific BPA degradation rate varied in the range 0.001-0.0066 min-1, while BPA percent degradation at 120 minutes of irradiation varied from 14 to 55%; TOC removal varied from 1.5 to 12.5%. Persistent degradation products were formed, and oxygen reactive species (1O2, oHO) showed to exhibit an important role during BPA degradation. The obtained quantum yield of BPA photolysis was 0.0075 mol BPA mol photons-1, determined from the experimental data through a mathematical model for BPA photolytic degradation versus time. With that aim a treatment system formed by a tubular reactor connected with a mixing tank with recirculation between them was considered; the tubular reactor was treated as a series of three associated continuous perfect mixing reactors (CSTR). Through statistical analysis of the experimental data for two responses (specific BPA degradation rate and BPA percent degradation at 120 minutes), the effects of the variables involved in BPA degradation (initial BPA concentration and specific rate of photon emission) were discussed.

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

Colloidal semiconductor quantum dots (QDs) have gained substantial interest as adjustable, bright and spectrally tunable fluorophores in the past decades. Besides their in-depth analyses in the scientific community, first industrial applications as color conversion and color enrichment materials were implemented. However, stability and processability are essential for their successful use in these and further applications. Methods to embed QDs into oxides or polymers can only partially solve this challenge. Recently, our group introduced the embedding of QDs into ionic salts, which holds several advantages in comparison to polymer or oxide-based counterparts. Both gas permeability and environmental-related degradation processes are negligible, making these composites an almost perfect choice of material. To evaluate this new class of QD-salt mixed crystals, a thorough understanding of the formation procedure and the final composites is needed. The present work is focused on embedding both aqueous-based and oil-based metal-chalcogenide QDs into several ionic salts and the investigations of their optical and chemical properties upon incorporation into the mixed crystals. QDs with well-known, reproducible and high-quality synthetic protocols are chosen as emissive species. CdTe QDs were incorporated into NaCl as host matrix by using the straightforward "classical" method. The resulting mixed crystals of various shapes and beautiful colors preserve the strong luminescence of the incorporated QDs. Besides NaCl, also borax and other salts are used as host matrices. Mercaptopropionic acid stabilized CdTe QDs can easily be co-crystallized with NaCl, while thioglycolic acid as stabilizing agent results in only weakly emitting powder-like mixed crystals. This challenge was overcome by adjusting the pH, the amount of free stabilizer and the type of salt used, demonstrating the reproducible incorporation of highest-quality CdTe QDs capped with thioglycolic acid into NaCl and KCl salt crystals. A disadvantage of the "classical" mixed crystallization procedure was its long duration which prevents a straightforward transfer of the protocol to less stable QD colloids, e.g., initially oil-based, ligand exchanged QDs. To address this challenge, the "Liquid-liquid-diffusion-assisted-crystallization" (LLDC) method is introduced. By applying the LLDC, a substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process opens the field of incorporating ligand-exchanged Cd-free QDs into NaCl matrices. To overcome the need for a ligand exchange, the LLDC can also be extended towards a two-step approach. In this modified version, the seed-mediated LLDC provides for the first time the ability to incorporate oil-based QDs directly into ionic matrices without a prior phase transfer. The ionic salts appear to be very tight matrices, ensuring the protection of the QDs from the environment. As one of the main results, these matrices provide extraordinary high photo- and chemical stability. It is further demonstrated with absolute measurements of photoluminescence quantum yields (PL-QYs), that the PL-QYs of aqueous CdTe QDs can be considerably increased upon incorporation into a salt matrix by applying the "classical" crystallization procedure. The achievable PL enhancement factors depend strongly on the PL-QYs of the parent QDs and can be described by the change of the dielectric surrounding as well as the passivation of the QD surface. Studies on CdSe/ZnS in NaCl and CdTe in borax showed a crystal-induced PL-QY increase below the values expected for the respective change of the refractive index, supporting the derived hypothesis of surface defect curing by a CdClx formation as one main factor for PL-QY enhancement. The mixed crystals developed in this work show a high suitability as color conversion materials regarding both their stability and spectral tunability. First proof-of-concept devices provide promising results. However, a combination of the highest figures of merit at the same time is intended. This ambitious goal is reached by implementing a model-experimental feedback approach which ensures the desired high optical performance of the used emitters throughout all intermediate steps. Based on the approach, a white LED combining an incandescent-like warm white with an exceptional high color rendering index and a luminous efficacy of radiation is prepared. It is the first time that a combination of this highly related figures of merit could be reached using QD-based color converters. Furthermore, the idea of embedding QDs into ionic matrices gained considerable interest in the scientific community, resulting in various publications of other research groups based on the results presented here. In summary, the present work provides a profound understanding how this new class of QD-salt mixed crystal composites can be efficiently prepared. Applying the different crystallization methods and by changing the matrix material, mixed crystals emitting from blue to the near infrared region of the electromagnetic spectrum can be fabricated using both Cd-containing and Cd-free QDs. The resulting composites show extraordinary optical properties, combining the QDs spectral tunability with the rigid and tight ionic matrix of the salt. Finally, their utilization as a color conversion material resulted in a high-quality white LED that, for the first time, combines an incandescent-like hue with outstanding optical efficacy and color rendering properties. Besides that, the mixed crystals offer huge potential in other high-quality applications which apply photonic and optoelectronic components.

Cette thèse porte sur l’étude de la transformation de polluants organiques à la surface du sol sous l’effet de la lumière. Deux principaux composés organiques ont été utilisés : une molécule modèle, la phénylbenzo-quinone (PhQ) ; et un pesticide de la famille des carbamates, le carbaryl. Nous avons travaillé sur différents supports : trois supports modèles (silice, sable de Fontainebleau et kaolinite) et sur un sol de la région d’Orange. La phototransformation a été réalisée en utilisant un dispositif qui simule le rayonnement solaire (l>300nm). L’étude des propriétés spectroscopiques de PhQ sur support solide a permis de montrer un élargissement de la bande d’absorption et des effets bathochrome et hyperchrome. Lors de l’irradiation, la concentration et l’épaisseur des films se sont avérés être des paramètres importants à considérer afin de tenir compte respectivement l’effet d’écran et le phénomène de diffusion. Une valeur limite de l’épaisseur égale à 100 μm a été déterminée afin de s’affranchir du processus de diffusion. Le mécanisme de transformation de PhQ s’est avéré être identique à celui observé dans l’eau avec la formation d’un unique produit, la 2-hydroxydibenzofuranne, et la mise en évidence de l’état excité triplet de PhQ. La présence d’eau influence la phototransformation du composé en augmentant la vitesse de transformation. Ceci s’explique par une modification des propriétés d’absorption du support humide qui favorise la pénétration de la lumière. Suite à cette première étude, un travail plus complexe a été entrepris sur la photodégradation du carbaryl à la surface de supports modèles. Le coefficient d’absorption molaire sur la kaolinite et le rendement quantique de transformation ont pu être déterminés pour le carbaryl et d’autres composés organiques. Ceci nous a permis de confirmer l’effet bathochrome, l’effet hyperchrome, ainsi que l’augmentation du rendement quantique : augmentation d’un facteur 10 pour le carbaryl. Les études cinétiques ont montré que la dégradation du carbaryl est effective sur tous les supports. A l’aide des propriétés physico-chimiques des supports, nous avons pu émettre l’hypothèse que la taille des particules contrôle la photodégradation. Celle-ci est plus efficace avec des particules de grande taille, du fait de la meilleure pénétration des photons. Enfin à l’aide d’une étude analytique poussée et de la mise en évidence de la formation de HO• et 1O2, nous avons proposé un mécanisme de photodégradation impliquant des réactions de PhotoFries, de photohydrolyse, de dimérisation et d’hydroxylation. Dans la deuxième partie des travaux sur le sol réel, un protocole original a été mis en oeuvre. Il consiste en un fractionnement préalable du sol suivi d’un traitement chimique afin d’atténuer l’impact de la matière organique. Il a été montré que la dégradation sur le sol et ses fractions est efficace et que la matière organique a un effet bénéfique, à faible concentration, et inhibiteur, à forte concentration, sur la transformation du carbaryl. De plus, le fractionnement a révélé que la photodégradation est d’autant plus importante que les fractions sont constituées de particules de grande taille. Enfin, la formation d’espèces réactives (HO• et 1O2) a été observée systématiquement et plus efficacement pour les fractions sans matière organique suggérant des processus de transformation attribuables à la partie minérale des supports. / This study focuses on the transformation of organic pollutants on soil surface under the influence of the light excitation. Two main organic compounds were used as model molecules, phenylbenzoquinone (PhQ) and a carbamate pesticide, carbaryl. We used several supports : three model supports (silica, sand of Fontainebleau and kaolinite) and a real soil of the region of Orange (France). The phototransformation was carried out using a device that simulates the solar radiation (l > 300 nm). The study of the spectroscopic features of PhQ on solid support shows a broad band of absorption that presents bathochromic and hyperchromic effects. During irradiation, the concentration and the thickness of film were found to be important parameters to be considered in order to avoid the screen as well as diffusion effect. The optimal value of the thickness was determined roughly to 100 μm in order to minimise the diffusion effect. The mechanism of transformation of PhQ is similar to that observed in aqueous solution with the formation of the unique photoproduct 2-hydroxybenzofuran. The process involves the triplet excited state of PhQ. After this work, the first studies are on the phototransformation of carbaryl and other pesticides on model supports. Furthermore, the molar absorption coefficient and quantum yield have been determined in order to confirm the bathochromic and hyperchromic effect and also the increase of the quantum yield (10 times for carbaryl). The degradation process was most effective when the particle size increases. Moreover, from the analytical studies the photodegradation mechanism was suggested involving several reactions such as photofries, photohydrolyse, dimerisation and hydroxylation. The second part of the present work was dedicated to the study on real soil. An original protocol had to be set up. It consisted on a prefractionation of soil followed by a chemical treatment to minimise the impact of organic matter. Concerning the phototransformation of carbaryl, it was shown that the degradation at the surface of soil and its fractions is effective and that the organic matter has a beneficial effect at low concentrations and inhibition effect at high concentrations. Furthermore, fractionation revealed that photodegradation is more important when the fractions are composed of large particles. Finally, the formation of reactive species (HO• and 1O2) was observed consistently and efficiently for fractions without organic matter suggesting transformation processes induced by the mineral part of the supports.

In this study, organic and polymeric fluorophores based on 2,4,6-triphenylpyridiene (TPP) structure were found to have the novel aggregation-induced emission enhancement (AIEE) property. For the small-mass fluorophores, TPP and cyano-functionalized TPP (TPP-CN) were prepared from the facile Chichibabin reaction and their AIEE properties were characterized by the emission behavior in solvent/nonsolvent pair. Solid samples of TPP and TPP-CN exhibit enhanced emission with increasing annealing time under solvent vapors, thus, both compounds have the characters of crystallization-induced emission enhancement (CIEE) behavior. For polymeric system, copolymers PTPPF containing alternative TPP and 9,9-dioctylfluorene units were prepared through Suzuki coupling and study on its fluorescence behavior also reveals its AIEE feature. The rigid polymer possesses high emission intensity in its dilute solution state and remains almost unchanged with increasing nonsolvent fraction. The solid sample was found to have a high quantum yield (ФF) of 70 %.