Search results for "Photochemical"
showing 10 items of 108 documents
Synthesis of a potent photoreactive acidic γ-secretase modulator for target identification in cells.
2012
Supramolecular self-assembly of amyloidogenic peptides is closely associated with numerous pathological conditions. For instance, Alzheimer´s disease (AD) is characterized by abundant amyloid plaques originating from the proteolytic cleavage of the amyloid precursor protein (APP) by β- and γ-secretases. Compounds named γ-secretase modulators (GSMs) can shift the substrate cleavage specificity of γ-secretase toward the production of non-amyloidogenic, shorter Aβ fragments. Herein, we describe the synthesis of highly potent acidic GSMs, equipped with a photoreactive diazirine moiety for photoaffinity labeling. The probes labeled the N-terminal fragment of presenilin (the catalytic subunit of …
Chemistry and Photochemistry of 2,6-Bis(2-hydroxybenzilidene)cyclohexanone. An Example of a Compound Following the Anthocyanins Network of Chemical R…
2014
The kinetics and thermodynamics of the 2,6-bis(2-hydroxybenzilidene)cyclohexanone chemical reactions network was studied at different pH values using NMR, UV-vis, continuous irradiation, and flash photolysis. The chemical behavior of the system partially resembles anthocyanins and their analogue compounds. 2,6-Bis(2-hydroxybenzilidene)cyclohexanone exhibits a slow color change from yellow to red styrylflavylium under extreme acidic conditions. The rate constant for this process (5 × 10(-5) s(-1)) is pH independent and controlled by the cis-trans isomerization barrier. However, the interesting feature is the appearance of the colorless compound, 7,8-dihydro-6H-chromeno[3,2-d]xanthene, isolat…
Macroalgal responses to ocean acidification depend on nutrient and light levels
2015
Ocean acidification may benefit algae that are able to capitalize on increased carbon availability for photosynthesis, but it is expected to have adverse effects on calcified algae through dissolution. Shifts in dominance between primary producers will have knock-on effects on marine ecosystems and will likely vary regionally, depending on factors such as irradiance (light vs. shade) and nutrient levels (oligotrophic vs. eutrophic). Thus experiments are needed to evaluate interactive effects of combined stressors in the field. In this study, we investigated the physiological responses of macroalgae near a CO2 seep in oligotrophic waters off Vulcano (Italy). The algae were incubated in situ …
Seagrass ecosystem response to long-term high CO2 in a Mediterranean volcanic vent
2014
We examined the long-term effect of naturally acidified water on a Cymodocea nodosa meadow growing at a shallow volcanic CO2 vent in Vulcano Island (Italy). Seagrass and adjacent unvegetated habitats growing at a low pH station (pH = 7.65 ± 0.02) were compared with corresponding habitats at a control station (pH = 8.01 ± 0.01). Density and biomass showed a clear decreasing trend at the low pH station and the below- to above-ground biomass ratio was more than 10 times lower compared to the control. C content and delta 13C of leaves and epiphytes were significantly lower at the low pH station. Photosynthetic activity of C. nodosa was stimulated by low pH as seen by the significant increase in…
Chemical and photochemical properties of chloroharmine derivatives in aqueous solutions
2015
Thermal and photochemical stability (ΦR), room temperature UV-vis absorption and fluorescence spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), quantum yields of hydrogen peroxide (ΦH2O2) and singlet oxygen (ΦΔ) production, and triplet lifetimes (τT) have been obtained for the neutral and protonated forms of 6-chloroharmine, 8-chloroharmine and 6,8-dichloroharmine, in aqueous media. When it was possible, the effect of pH and oxygen concentration was evaluated. The nature of electronic transitions of protonated and neutral species of the three investigated chloroharmines was established using Time-Dependent Density Functional Theory (TD-DFT) calculations. The impact of all the fo…
Acclimation Potential to High Irradiance of Two Cultivars of Watermelon
2000
The acclimation potential to high irradiance of two cultivars of watermelon, Reina de Corazones and Toro, calculated as the ratio of sun vs. shade activities of O2− and H2O2 scavenging enzymes and non-radiative energy dissipation, was similar. However, Reina de Corazones exhibited a higher capacity in absolute terms for photoprotection (harmless dissipation of absorbed light energy at PS 2 and ascorbate and O2− and H2O2 scavenging enzymes) suggesting a larger resistance of this cultivar to high irradiance. This could be seen as smaller decreases in fruit productivity and in lower oxidative injury as probed by malondialdehyde content in sun plants of Reina de Corazones than in Toro plants. A…
Retrieval of sun-induced fluorescence using advanced spectral fitting methods
2015
Abstract The FLuorescence EXplorer (FLEX) satellite mission, candidate of ESA's 8th Earth Explorer program, is explicitly optimized for detecting the sun-induced fluorescence emitted by plants. It will allow consistent measurements around the O2-B (687 nm) and O2-A (760 nm) bands, related to the red and far-red fluorescence emission peaks respectively, the photochemical reflectance index, and the structural-chemical state variables of the canopy. The sun-induced fluorescence signal, overlapped to the surface reflected radiance, can be accurately retrieved by employing the powerful spectral fitting technique. In this framework, a set of fluorescence retrieval algorithms optimized for FLEX ar…
Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.
2013
New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic abso…
On the Intrinsically Low Quantum Yields of Pyrimidine DNA Photodamages: Evaluating the Reactivity of the Corresponding Minimum Energy Crossing Points
2020
The low quantum yield of photoformation of cyclobutane pyrimidine dimers and pyrimidine-pyrimidone (6-4) adducts in DNA bases is usually associated with the presence of more favorable nonreactive decay paths and with the unlikeliness of exciting the system in a favorable conformation. Here, we prove that the ability of the reactive conical intersection to bring the system either back to the absorbing conformation or to the photoproduct must be considered as a fundamental factor in the low quantum yields of the mentioned photodamage. In support of the proposed model, the one order of magnitude difference in the quantum yield of formation of the cyclobutane thymine dimer with respect to the t…
Pyrrolo[3,4-h]quinolinones a new class of photochemotherapeutic agents
2011
Abstract Pyrrolo[3,4- h ]quinolin-2-ones were synthesized as nitrogen isosters of the angular furocoumarin angelicin, with the aim of obtaining new photochemotherapeutic agents with increased antiproliferative activity and lower undesired toxic effects. A versatile synthetic pathway was approached to allow the isolation of derivatives of the new ring system with a good substitution pattern on the pyrrole moiety. Photobiological screenings of the new compounds revealed a potent phototoxic effect and a great UVA dose dependence, reaching IC 50 values at submicromolar level. The induced cellular photocytotoxicity was related to apoptosis with the involvement of mitochondria and lysosomes, alte…