Photosynthetic properties of three Brazilian seaweeds

Photosynthetic performance of distinct marine macroalgae, Ulva fasciata Delile (green alga), Lobophora variegata (J. V. Lamouroux) Womersley ex E. C. Oliveira (brown alga), and Plocamium brasiliensis (Greville) M. A. Howe & W. R. Taylor (red alga), were compared using a pulse amplitude-modulated fluorometer. The maximum quantum yield (Fv/Fm) ranged from 0.80 to 0.51, and the lowest value was found in P. brasiliensis. Under 400 µmol photons m-2 s-1 irradiance, the highest value of photochemical quenching (qP = 0.92 ± 0.13) was observed for U. fasciata. The red alga P. brasiliensis dissipated high amounts of excitation energy (qN = 0.56 ± 0.09), resulting in relatively low values for the effective quantum yield of PS-II (0.23 ± 0.04), as well as for the relative electron transport rate (3.3 ± 0.7). The high photosynthetic potential found for U. fasciata partially explains the species ability for rapid growth and high productivity.

Photosynthetic responses of four tropical tree species grown under gap and understorey conditions in a semi-deciduous forest

Leaf CO2 assimilation (A) as a function of photosynthetic photon flux density (Q) or intercellular CO2 concentration (Ci) and chlorophyll fluorescence measurements were carried out on four tropical woody species growing in forest gap and understorey (Bauhinia forficata Link. and Guazuma ulmifolia Lam. as pioneers, and Hymenaea courbaril L. and Esenbeckia leiocarpa Engl. as non-pioneers). Chlorophyll fluorescence indicated similar acclimation capacities of photochemical apparatus to contrasting light environments irrespective to plant species. Maximum CO2 assimilation and quantum yield derived from A/Q curves indicated higher photosynthetic capacity in pioneer than in non-pioneer species in forest gap. However, the differences among species did not show a straightforward relation with their successional status regarding data derived from A/Q curves under understorey conditions. Both successional groups are able to sustain positive carbon balance under contrasting natural light availabilities, modifying photochemical and biochemical photosynthetic traits with similar phenotypic plasticity capacity.

Développement de nouveaux matériaux conjugués aux propriétés opto-électroniques modulables : de l’électrochromisme à la fluorescence.

La thèse est divisée en deux parties, soit le texte principal et les annexes afin d'alléger la taille des documents.

Synthesis and characterisation of novel nitrogen and fluorine containing spirobifluorene derivatives for electronic applications and crystal engineering

Among organic materials, spirobifluorene derivatives represent a very attractive class of materials for electronic devices. These compounds have high melting points, glass transitions temperatures and morphological stability, which makes these materials suitable for organic electronic applications. In addition, some of spirobifluorenes can form porous supramolecular associations with significant volumes available for the inclusion of guests. These molecular associations based on the spirobifluorenes are noteworthy because they are purely molecular analogues of zeolites and other microporous solids, with potential applications in separation, catalysis, sensing and other areas.

Effects of N supply on the accumulation of photosynthetic pigments and photoprotectors in Gracilaria tenuistipitata (Rhodophyta) cultured under UV radiation

We have studied the effects of nitrate supply under photosynthetic active radiation (PAR) plus ultraviolet radiation (UVR) exposure on photosynthetic pigments (chlorophyll a and carotenoids), photoprotective UV screen mycosporine-like amino acids (MAAs), and photosynthetic parameters, including the maximum quantum yield (F(v)/F(m)) and electron transport rate (ETR) on the red agarophyte Gracilaria tenuistipitata. Apical tips of G. tenuistipitata were cultivated under ten different concentrations of NO(3)(-) for 7 days. It has been shown that G. tenuistipitata cultured under laboratory conditions has the ability to accumulate high amounts of MAAs following a nitrate concentration-dependent manner under PAR+UVR. Two MAAs were identified, shinorine and porphyra-334. The relative concentration of the first increased under high concentrations of nitrate, while the second one decreased. The presence of antheraxanthin is reported for the first time in this macro-algae, which also contains zeaxanthin, lutein, and beta-carotene. The accumulation of pigments, photoprotective compounds, and photosynthetic parameters of G. tenuistipitata is directly related to N availability. All variables decreased under low N supplies and reached constant maximum values with supplements higher than 0.5 mM NO(3)(-). Our results suggest a high potential to acclimation and photoprotection against stress factors (including high PAR and UVR) directly related to N availability for G. tenuistipitata.

Spectroscopic investigations of OH- influence on near-infrared fluorescence quenching of Yb3+/Tm3+ co-doped sodium-metaphosphate glasses

Energy transfer processes were studied in two sets of Yb3+ and Tm3+ co-doped sodium-metaphosphate glasses, prepared in air and nitrogen atmospheres. Using Forster, Dexter, and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were energy migration among Yb3+ ions, cross-relaxations between Yb3+ and Tm3+ ions, and interactions with OH- radicals. The results indicated that Yb -> Tm energy transfer favors 1.8 mu m emissions, and there is no evidence of concentration quenching up to 2% Tm2O3 doping. As expected, samples prepared in nitrogen atmosphere present higher fluorescence quantum efficiency than those prepared in air, and this feature is specially noted in the near-infrared region, where the interaction with the OH- radicals is more pronounced. (c) 2007 Published by Elsevier B.V.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Taurine bromamine: A potent oxidant of tryptophan residues in albumin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Assessing the role of vertical leaves within the photosynthetic function of Styrax camporum under drought conditions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photoacclimation in a tropical population of Cladophora glomerata (L.) Kützing 1843 (Chlorophyta) from southeastern Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Daily dynamics of photosynthesis of the freshwater red alga Sirodotia delicatula (Batrachospermales, Rhodophyta)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

Light-related photosynthetic characteristics of freshwater rhodophytes

Photosynthetic characteristics in response to irradiance were analysed in 21 field and culture populations of thirteen freshwater red algal species applying two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves indicated adaptations to low irradiances in all species analysed, essentially characterized by occurrence of photoinhibition, low values of the saturation parameter (I-k < 225 mu mol m(-2) s(-1)) and compensation irradiance (I-c < 20 mu mol m(-2) s(-1)) and relatively high values of the effective quantum yield of photosystem II (Delta F/F'(m) >= 45). These characteristics have been reported in freshwater red algae and were confirmed from data based on the two techniques, indicating they are typically shade-adapted plants. on the other hand, some species (e.g. Batrachospermum delicatulum) can tolerate high irradiances (up to 2400 mu mol m(-2) s(-1)), suggesting they have mechanisms that enable them to avoid photodarnage of the photosynthetic apparatus. One of these mechanisms is the increase in dissipation of excessive energy captured by reaction centres after exposure to continuous irradiance, as reflected by the non-photochemical quenching fluorescence parameter in dark/light induction curves. Photo-inhibition occurred in all algae tested by both techniques. Light acclimation was evident particularly in field populations, as revealed by lower values of the saturation parameter (Ik) and the compensation irradiance (I-c) and higher values of Delta F/F'(m) in algae under low irradiances (shaded or heavily shaded stream segments), and vice-versa. Forms living within the boundary layer (e.g. crusts), in a region of reduced current velocity, tended to be more shade-adapted than semi-erect plants (e.g. non-mucilaginous or mucilaginous filaments), as indicated by highest values of photosynthetic efficiency (alpha = 0.31) and effective quantum yield (Delta F/F'(m) = 0.88) under natural conditions. Higher photo- synthetic rates (P-max) for the same species or population were observed under culture than field conditions when measured with the oxygen evolution technique, whereas the opposite trend was observed using chlorophyll fluorescence. (c) 2005 Elsevier B.V. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Light-related photosynthetic characteristics of lotic macroalgae

Photosynthetic characteristics in response to irradiance were analysed in 42 populations of 33 macroalgal species by two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves based on the two techniques indicated adaptations to low irradiance reflected by low saturation values, high to moderate values of photosynthetic efficiency (alpha) and photoinhibition (beta), for Bacillariophyta and Rhodophyta, which suggests they are typically shade-adapted algae. In contrast, most species of Chlorophyta were reported as sun adapted algae, characterized by high values of I-k and low of alpha, and lack of or low photoinhibition. Cyanophyta and Xanthophyta were intermediate groups in terms of light adaptations. Photoinhibition was observed in variable degrees in all algal groups, under field and laboratory conditions, which confirms that it is not artificially induced by experimental conditions, but is rather a common and natural phenomenon of the lotic macroalgae. Low values of compensation irradiance (I-c) were found, which indicate that these algae can keep an autotrophic metabolism even under very low irradiances. High ratios (>2) of photosynthesis/respiration were found in most algae, which indicates a considerable net gain. These two physiological characteristics suggest that macroalgae may be important primary producers in lotic ecosystems. Saturation parameters (I-k and I-s) occurred in a relatively narrow range of irradiances (100-400 mumol photons m(-2) s(-1)), with some exceptions (higher in some filamentous green algae or lower in red algae). These parameters were way below the irradiances measured at collecting sites for most algae, which means that most of the available light energy was not photochemically converted via photosynthesis. Acclimation to ambient PAR was observed, as revealed by lower values of I-k and I-c and higher values of alpha and quantum yield in algae from shaded streams, and vice versa. Forms living within the boundary layer (crusts) showed responses of shade-adapted species and had the highest values of P-max, alpha and quantum yield, whereas the opposite trend was observed in gelatinous forms (colonies and. laments). These results suggests adaptation to the light regime rather than functional attributes related to the growth form.