Molecular-level transformations of lignin during photo-oxidation and biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-04-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo-oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo-oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Energy transfer mechanisms in photobiological reactions. Final report, 1 April 1960--31 March 1979. [Photodynamic processes in selected biomolecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spikes, J.D.

1979-03-31

This project was concerned primarily with studies of the mechanisms of the sensitized photooxidation of selected biomolecules using a variety of phtosensitizers. Such reactions are often termed photodynamic processes. In particular we have carried out steady-state kinetic studies, flash photolysis and spectral studies, and product formation studies of the sensitized photooxidation of the five susceptible amino acids (cycteine, histidine, methonine, tryptophan, and tyrosine) and their derivatives, as well as purines and pyrimidines. A number of studies were also carried out on the mechanisms of the photodynamic inactivation of enzymes (trypsin, ribonuclease, lysozyme). Mechanism of photosensitization were studied using a varietymore » of sensitizers including flavins, porphyrins, and a number of synthetic dyes (substituted fluoresceins, acridines, thyazines).« less

Role of relative humidity and Cd/Zn stoichiometry in the photo-oxidation process of cadmium yellows (CdS/Cd1-xZnxS) in oil paintings.

PubMed

Monico, Letizia; Chieli, Annalisa; De Meyer, Steven; Cotte, Marine; de Nolf, Wout; Falkenberg, Gerald; Janssens, Koen; Romani, Aldo; Miliani, Costanza

2018-06-06

Cadmium yellows (CdYs) refer to a family of cadmium sulfide pigments which have been widely used by artists since the late 19th c. Despite being considered stable, they are suffering from discoloration in iconic paintings, such as Joy of Life by Matisse, Flowers in a blue vase by Van Gogh and the Scream by Munch, most likely due to the formation of CdSO₄·nH₂O. Questions about what the factors driving the CdYs degradation are and how they affect the overall process are still open. Here, we study a series of oil mock-up paints made of CdYs of different stoichiometry (CdS/Cd₀.₇₆Zn₀.₂₄S) and crystalline structure (hexagonal/cubic) before and after aging at variable relative humidity under exposure to light and in darkness. Synchrotron-based X-ray methods combined with UV-Visible and FTIR spectroscopies show that: (i) Cd₀.₇₆Zn₀.₂₄S is more susceptible to photo-oxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. (ii) The photo-oxidation of CdS/Cd₀.₇₆Zn₀.₂₄S to CdSO₄·nH₂O is triggered by moisture. (iii) The nature of alteration products depends on the aging conditions and Cd/Zn stoichiometry. Based on our findings, we propose a scheme for the mechanism of the photocorrosion process and photocatalytic activity of CdY pigments in the oil binder. Overall, our results form a reliable basis for understanding the degradation of CdS-based paints of artworks and contribute towards developing better ways of preserving them for future generations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-oxidation of Nitrophenols in the Aqueous Phase: Reaction Kinetics, Mechanistic Insights, and Evolution of Light Absorption

NASA Astrophysics Data System (ADS)

Hems, R.; Abbatt, J.

2017-12-01

Nitrophenols are a class of water soluble, light absorbing compounds which can make up a significant fraction of biomass burning brown carbon. The atmospheric lifetime and aging of these compounds can have important implications for their impact on climate through the aerosol direct effect. Recent studies have shown that brown carbon aerosols can be bleached of their colour by direct photolysis and photo-oxidation reactions on the timescale of hours to days. However, during aqueous phase photo-oxidation of nitrophenol compounds light absorption is sustained or enhanced, even after the parent nitrophenol molecule has been depleted. In this work, we use online aerosol chemical ionization mass spectrometry (aerosol-CIMS) to investigate the aqueous phase photo-oxidation mechanism and determine the second order rate constants for the reaction of OH radicals with three commonly detected nitrophenol compounds: nitrocatechol, nitroguaiacol, and dinitrophenol. These nitrophenol compounds are found to have aqueous phase lifetimes with respect to oxidation by the OH radical ranging between 5 - 11 hours. Our results indicate that functionalization of the parent nitrophenol molecule by addition of hydroxyl groups leads to the observed absorption enhancement. Further photo-oxidation forms breakdown products that no longer absorb significantly in the visible light range.

Impact of nano/micron vegetable carbon black on mechanical, barrier and anti-photooxidation properties of fish gelatin film.

PubMed

Ding, Junsheng; Wu, Xiaomeng; Qi, Xiaona; Guo, Heng; Liu, Anjun; Wang, Wenhang

2018-05-01

In this paper, two kinds of commonly used vegetable carbon black (VCB, 3000 mesh; nano) at 50 g kg -1 concentration (based on dried gelatin) were added to 48 g kg -1 of fish gelatin (GEL) solutions and their effects on mechanical, barrier and anti-photooxidation properties of GEL films were investigated. From the SEM images, it was shown that compared with 3000 mesh VCB (1-2 μm), nano VCB (100-200 nm) made the microstructure of GEL film more compact and more gelatin chains were cross-linked by nano VCB. The addition of nano VCB significantly increased gelatin film strength with the greatest tensile strength of 52.589 MPa and stiffness with the highest Young's modulus of 968.874 MPa, but led to the reduction of film elongation. Also, the VCB presence significantly improved water vapour and oxygen barrier properties of GEL film. Importantly, nano VCB increased GEL film with better UV barrier property due to its stronger UV absorption nature when compared with micron VCB. This property could help in the preservation of oil samples in the photooxidation accelerated test. With improved properties, the nano VCB-reinforced GEL film may have great potential for application in the edible packaging field, especially for the anti-photooxidation property. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Photooxidation of the cytochrome b-559 in the presence of various substituted 2-anilinothiophenes and of some other compounds, in Chlamydomonas reinhardtii.

PubMed

Maroc, J; Garnier, J

1979-11-08

Five substituted 2-anilinothiophenes and two substituted carbonylcyanide-phenylhydrazones were comparatively studied with respect to their capacities for inducing photooxidation of the cytochrome b-559 in chloroplast fragments and in whole cells of Chlamydomonas reinhardtii (wild type and P-700-lacking mutant Fl 5). In addition, some other compounds: antimycin A, picric acid, tetraphenylboron and NH4Cl were also tested. Cytochrome b-559 photooxidations were clearly observed in the presence of 2-(3-chloro-4-trifluoromethyl)anilino-3,5-dinitrothiophene (ANT 2p), 2-(3,4,5-trichloro)anilino-3,5-dinitrothiophene (ANT 2s), 2-(4-chloro)anilino-3,5-dinitrothiophene and, with greater amplitudes, in the presence of carbonylcyanide-p-trifluoromethoxyphenylhydrazone and carbonylcyanide-m-chlorophenylhydrazone, both in whole cells and in chloroplast fragments. Picric acid, antimycin A and tetraphenylboron were also able to induce cytochrome b-559 photooxidation in chloroplast fragments, but not in whole cells. In the wild type, the highest photoinduced redox changes were 1.1 (carbonylcyanide-p-trifluoromethoxyphenylhydrazone, carbonylcyanide-m-chlorophenyl-hydrazone) and 0.6 (ANT 2p, ANT 2s) mumol of oxidized cytochrome b-559/1 mmol of chlorophyll, corresponding to 40% and 23% of the redox changes which could be induced chemically. All these cytochrome b-559 photooxidations, the greater part of which was inhibited by 3-(3,4-dichloropheny)-1,1-dimethylurea and occurred in the mutant Fl 5, appeared to be mainly Photosystem II-dependent reactions. But 3-(3,4-dichlorophenyl)-1,1-dimethylurea-insensitive Photosystem I-dependent photooxidations of cytochrome b-559 occurred also in the wild type. On the other hand, 2-(4-dimethylamine)-anilino-3,5-dinitrothiophene, 2-N-methyl-(3-chloro-4-trifluoromethyl)anilino-3,5-dinitrothiophene and NH4Cl did not induce any cytochrome b-559 photooxidation. These results were discussed taking in consideration the nature of the molecular substitutions of the various tested substances and their respective acceleration of the deactivation reactions of the water-splitting enzyme system Y of photosynthesis capacities which had been defined elsewhere by Renger (Renger, G. (1972) Biochim. Biophys. Acta 256, 428-439) for spinach chloroplasts. Like the acceleration of the deactivation reactions of the water-splitting enzyme system Y effect, the capacity for inducing the cytochrome b-559 photooxidation appeared dependent on the acidity of the NH group and on the number of halogenous substituents in the aromatic ring of the molecule. The greatest action towards cytochrome b-559 photooxidation was obtained with the most active acceleration of the deactivation reactions of the water-splitting enzyme system Y agents: carbonylcyanide-p-trifluoromethoxyphenylhydrazone, ANT 2p and ANT 2s.

Sex-related differences in photoinhibition, photo-oxidative stress and photoprotection in stinging nettle (Urtica dioica L.) exposed to drought and nutrient deficiency.

PubMed

Simancas, Bárbara; Juvany, Marta; Cotado, Alba; Munné-Bosch, Sergi

2016-03-01

Dimorphic plant species can show distinct nutrient needs due to sex-related differences in nutrient allocation to reproductive structures, which can potentially affect their sensitivity to photoinhibition and photo-oxidative stress. Here, we investigated sex-related differences in the extent of photo-oxidative stress in male and female individuals of U. dioica exposed to a combination of severe drought and nutrient starvation. Male and female individuals of U. dioica subject to severe drought stress were exposed to various levels of nutrient availability. First, a set of plants grown under field conditions and exposed to summer drought was used to test the effects of nutrient supply (given as NPK fertilizer). Secondly, the effects of various phosphate concentrations in the nutrient solution were tested in drought-stressed potted plants. The Fv/Fm ratio (maximum efficiency of PSII photochemistry), photoprotection capacity (levels of carotenoids, including the xanthophyll cycle, and vitamins C and E), and the extent of lipid peroxidation (hydroperoxide levels) were measured. Results showed that an application of the NPK fertilizer to the soil had a positive effect on drought-stressed plants, reducing the extent of lipid peroxidation in both males and females. P deficiency led to residual photoinhibition, as indicated by significant reductions in the Fv/Fm ratio, and enhanced lipid peroxidation in females, but not in males. We conclude that (i) increased nutrient availability in the soil can alleviate photo-oxidative stress in drought-stressed U. dioica plants, and (ii) U. dioica plants show sexual secondary dimorphism in terms of photoinhibition and photo-oxidative stress, but this is only apparent when stress infringed on plants is very severe. Copyright © 2016 Elsevier B.V. All rights reserved.

Inosine Can Increase DNA's Susceptibility to Photo-oxidation by a RuII Complex due to Structural Change in the Minor Groove.

PubMed

Keane, Páraic M; Hall, James P; Poynton, Fergus E; Poulsen, Bjørn C; Gurung, Sarah P; Clark, Ian P; Sazanovich, Igor V; Towrie, Michael; Gunnlaugsson, Thorfinnur; Quinn, Susan J; Cardin, Christine J; Kelly, John M

2017-08-01

Key to the development of DNA-targeting phototherapeutic drugs is determining the interplay between the photoactivity of the drug and its binding preference for a target sequence. For the photo-oxidising lambda-[Ru(TAP) 2 (dppz)] 2+ (Λ-1) (dppz=dipyridophenazine) complex bound to either d{T 1 C 2 G 3 G 4 C 5 G 6 C 7 C 8 G 9 A 10 } 2 (G9) or d{TCGGCGCCIA} 2 (I9), the X-ray crystal structures show the dppz intercalated at the terminal T 1 C 2 ;G 9 A 10 step or T 1 C 2 ;I 9 A 10 step. Thus substitution of the G 9 nucleobase by inosine does not affect intercalation in the solid state although with I9 the dppz is more deeply inserted. In solution it is found that the extent of guanine photo-oxidation, and the rate of back electron-transfer, as determined by pico- and nanosecond time-resolved infrared and transient visible absorption spectroscopy, is enhanced in I9, despite it containing the less oxidisable inosine. This is attributed to the nature of the binding in the minor groove due to the absence of an NH 2 group. Similar behaviour and the same binding site in the crystal are found for d{TTGGCGCCAA} 2 (A9). In solution, we propose that intercalation occurs at the C 2 G 3 ;C 8 I 9 or T 2 G 3 ;C 8 A 9 steps, respectively, with G 3 the likely target for photo-oxidation. This demonstrates how changes in the minor groove (in this case removal of an NH 2 group) can facilitate binding of Ru II dppz complexes and hence influence any sensitised reactions occurring at these sites. No similar enhancement of photooxidation on binding to I9 is found for the delta enantiomer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-oxidation degradation mechanisms in P3HT for organic solar cells: Insights from first-principles simulations

NASA Astrophysics Data System (ADS)

Leung, Kevin; Sai, Na; Zador, Judit; Henkelman, Graeme

2014-03-01

Photo-oxidation is one of the leading chemical degradation mechanisms in polymer solar cells. In this work, using hybrid density functional theory and periodic boundary condition, we investigate reaction pathways that may lead to the sulfur oxidation in poly(3-hexylthiophene)(P3HT) as a step toward breaking the macromolecule backbone. We calculate energy barriers for reactions of P3HT backbone with oxidizing radicals suggested by infrared spectroscopy (IR) and XPS studies. Our results strongly suggest that an attack of hydroxyl radical on sulfur as proposed in the literature is unlikely to be thermodynamically favored. On the other hand, a reaction between the alkylperoxyl radical and the polymer backbone may provide low barrier reaction pathways to photo-oxidation of conjugated polymers with side chains. Our work paves way for future studies using ab-initio calculations in a condensed phase setting to model complex chemical reactions relevant to photochemical stability of novel polymers. Supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award #DE-SC0001091.

Tracing nanoparticles and photosensitizing molecules at transmission electron microscopy by diaminobenzidine photo-oxidation.

PubMed

Malatesta, M; Pellicciari, C; Cisterna, B; Costanzo, M; Galimberti, V; Biggiogera, M; Zancanaro, C

2014-04-01

During the last three decades, diaminobenzidine photo-oxidation has been applied in a variety of studies to correlate light and electron microscopy. Actually, when a fluorophore is excited by light, it can induce the oxidation of diaminobenzidine into an electron-dense osmiophilic product, which precipitates in close proximity to the fluorophore, thereby allowing its ultrastructural detection. This method has very recently been developed for two innovative applications: tracking the fate of fluorescently labeled nanoparticles in single cells, and detecting the subcellular location of photo-active molecules suitable for photodynamic therapy. These studies established that the cytochemical procedures exploiting diaminobenzidine photo-oxidation represent a reliable tool for detecting, inside the cells, with high sensitivity fluorescing molecules. These procedures are trustworthy even if the fluorescing molecules are present in very low amounts, either inside membrane-bounded organelles, or at the surface of the plasma membrane, or free in the cytosol. In particular, diaminobenzidine photo-oxidation allowed elucidating the mechanisms responsible for nanoparticles internalization in neuronal cells and for their escape from lysosomal degradation. As for the photo-active molecules, their subcellular distribution at the ultrastructural level provided direct evidence for the lethal multiorganelle photo-damage occurring after cell photo-sensitization. In addition, DAB photo-oxidized samples are suitable for the ultrastructural detection of organelle-specific molecules by post-embedding gold immunolabeling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

DOE PAGES

He, Feng; Zhao, Weirong; Liang, Liyuan; ...

2014-11-11

Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, CO 3 2-, NO 3 -] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h -1) in the presence of bothmore » HCO 3 2- and NO 3 -, whereas HCO 3 2-, NO 3 -, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h -1). Using scavengers and enhancers for singlet oxygen ( 1O 2) and hydroxyl (HO ∙ ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO 3 ∙-) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO 3 ∙- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.« less

Pt(ii) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes.

PubMed

Casado-Sánchez, Antonio; Gómez-Ballesteros, Rocío; Tato, Francisco; Soriano, Francisco J; Pascual-Coca, Gustavo; Cabrera, Silvia; Alemán, José

2016-07-12

A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed.

Ranking mechanical pulps for their potential to photoyellow

Treesearch

Umesh P. Agarwal

2000-01-01

Recently found experimental evidence has provided strong support for an alternative photoyellowing mechanism that suggests that pulp- photoyellowing occurs due to direct photooxidation of hydroquinones (present in mechanical pulps) top-quinones. Because hydroquinones were found to be present in pulps, it may be possible to quantify them. Quantification of mechanical-...

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Modelling of polymer photodegradation for solar cell modules

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1981-01-01

A computer program developed to model and calculate by numerical integration the varying concentrations of chemical species formed during photooxidation of a polymeric material over time, using as input data a choice set of elementary reactions, corresponding rate constants and a convenient set of starting conditions is evaluated. Attempts were made to validate the proposed mechanism by experimentally monitoring the photooxidation products of small liquid alkane which are useful starting models for ethylene segments of polymers like EVA. The model system proved in appropriate for the intended purposes. Another validation model is recommended.

Molecular-Level Transformations of Lignin During Photo-Oxidation and Biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-05-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo- oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo- oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles

DOE PAGES

Muuronen, Mikko; Parker, Shane M.; Berardo, Enrico; ...

2016-12-07

Here, we present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO 2 nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron–proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S 1 potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron–hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances inmore » NAMD methods and emphasize the importance of explicit simulation of electronic excitations.« less

Functionalizing carbon nitride with heavy atom-free spin converters for enhanced 1 O 2 generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Wenting; Han, Congcong; Zhang, Qinhua

advanced photosensitizers for singlet oxygen (1O2) generation. However, the intersystem crossing (ISC) process is quite insufficient in carbon nitride, limiting the 1O2 generation. Here, we report a facile and general strategy to confined benzophenone as a heavy atom-free spin converter dopant in carbon nitride via the facile copolymerization. With proper energy level matching between the heavy atom-free spin converter and various ligands based on carbon nitride precursors, the proper combination can decrease the singlet-triplet energy gap (DEST) and hence generate 1O2 effectively. Due to its significant and selectivity for 1O2 generation, the as-prepared carbon nitride-based photosensitizer shows a high selectivemore » photooxidation activity for 1,5-dihydroxy-naphthalene (1,5-DHN). The product yield reached 71.8% after irradiation for 60 min, which was higher than that of cyclometalated PtII complexes (53.6%) in homogeneous photooxidation. This study can broaden the application of carbon nitride in the field of selective heterogeneous photooxidation due to simple operation, low cost, and high efficiency, making it a strong candidate for future industrialization.« less

Zeaxanthin Accumulation in the Absence of a Functional Xanthophyll Cycle Protects Chlamydomonas reinhardtii from Photooxidative Stress

PubMed Central

Baroli, Irene; Do, An D.; Yamane, Tomoko; Niyogi, Krishna K.

2003-01-01

Xanthophylls participate in light harvesting and are essential in protecting the chloroplast from photooxidative damage. To investigate the roles of xanthophylls in photoprotection, we isolated and characterized extragenic suppressors of the npq1 lor1 double mutant of Chlamydomonas reinhardtii, which lacks zeaxanthin and lutein and undergoes irreversible photooxidative bleaching and cell death at moderate to high light intensities. Here, we describe three suppressor strains that carry point mutations in the coding sequence of the zeaxanthin epoxidase gene, resulting in the constitutive accumulation of zeaxanthin in a range of concentrations. The presence of zeaxanthin in these strains was sufficient to prevent photooxidative damage in the npq1 lor1 background. The size of the light-harvesting antenna in the suppressors decreased in high light in a manner that was proportional to the relative content of zeaxanthin, with the strain having the most zeaxanthin showing a severe reduction in levels of the major light-harvesting complex II proteins in high light. We show that the effect of constitutive zeaxanthin on light harvesting is not the main cause of increased photoprotection, because in the absence of zeaxanthin, a strain with a smaller light-harvesting antenna showed only minor protection against photobleaching in high light. Furthermore, the zeaxanthin-accumulating suppressors were able to tolerate higher levels of exogenous reactive oxygen than their parental strain under conditions that did not affect light harvesting. Our results are consistent with an antioxidant role of zeaxanthin in the quenching of singlet oxygen and/or free radicals in the thylakoid membrane in vivo. PMID:12671093

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Evaluation of Aromatic Oxidation Reactions in Seven Chemical Mechanisms with an Outdoor Chamber

EPA Science Inventory

Simulations using seven chemical mechanisms are intercompared against O₃, NO_x and hydrocarbon data from photooxidation experiments conducted at the University of North Carolina outdoor smog chamber. The mechanisms include CB4–2002, CB05, CB05-TU, a CB05 vari...

Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Bloss, C.; Wagner, V.; Jenkin, M. E.; Volkamer, R.; Bloss, W. J.; Lee, J. D.; Heard, D. E.; Wirtz, K.; Martin-Reviejo, M.; Rea, G.; Wenger, J. C.; Pilling, M. J.

2005-03-01

The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE) to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Bloss, C.; Wagner, V.; Jenkin, M. E.; Volkamer, R.; Bloss, W. J.; Lee, J. D.; Heard, D. E.; Wirtz, K.; Martin-Reviejo, M.; Rea, G.; Wenger, J. C.; Pilling, M. J.

2004-09-01

The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature has been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE) to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

NASA Astrophysics Data System (ADS)

Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

2014-09-01

Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

PubMed

Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

2015-01-01

A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

Short-term regulation and alternative pathways of photosynthetic electron transport in Hibiscus rosa-sinensis leaves.

PubMed

Trubitsin, Boris V; Vershubskii, Alexey V; Priklonskii, Vladimir I; Tikhonov, Alexander N

2015-11-01

In this work, using the EPR and PAM-fluorometry methods, we have studied induction events of photosynthetic electron transport in Hibiscus rosa-sinensis leaves. The methods used are complementary, providing efficient tools for in situ monitoring of P700 redox transients and photochemical activity of photosystem II (PSII). The induction of P700(+) in dark-adapted leaves is characterized by the multiphase kinetics with a lag-phase, which duration elongates with the dark-adaptation time. Analyzing effects of the uncoupler monensin and artificial electron carrier methylviologen (MV) on photooxidation of P700 and slow induction of chlorophyll a fluorescence (SIF), we could ascribe different phases of transient kinetics of electron transport processes in dark-adapted leaves to the following regulatory mechanisms: (i) acceleration of electron transfer on the acceptor side of PSI, (ii) pH-dependent modulation of the intersystem electron flow, and (iii) re-distribution of electron fluxes between alternative (linear, cyclic, and pseudocyclic) pathways. Monensin significantly decreases a level of P700(+) and inhibits SIF. MV, which mediates electron flow from PSI to O2 with consequent formation of H2O2, promotes a rapid photooxidation of P700 without any lag-phase peculiar to untreated leaves. MV-mediated water-water cycle (H2O→PSII→PSI→MV→O2→H2O2→H2O) is accompanied by generation of ascorbate free radicals. This suggests that the ascorbate peroxidase system of defense against reactive oxygen species is active in chloroplasts of H. rosa-sinensis leaves. In DCMU-treated chloroplasts with inhibited PSII, the contribution of cyclic electron flow is insignificant as compared to linear electron flow. For analysis of induction events, we have simulated electron transport processes within the framework of our generalized mathematical model of oxygenic photosynthesis, which takes into account pH-dependent mechanisms of electron transport control and re-distribution of electron fluxes between alternative pathways. The model adequately describes the main peculiarities of P700(+) induction and dynamics of the intersystem electron transport. Copyright © 2015 Elsevier B.V. All rights reserved.

Photooxidation of dicarboxylic acids—Part I: Effects of inorganic ions on degradation of azelaic acid

NASA Astrophysics Data System (ADS)

Yang, Liming; Ray, Madhumita B.; Yu, Liya E.

In this paper, the first of a two-part series, effects of chloride, sulfate, and nitrate ions and pH on photooxidation of azelaic acid were investigated in an aqueous system. Nitrate ions play the major role in accelerating photooxidation of azelaic acid by increasing rad OH concentration, while chloride ions consume rad OH concentration and retard photooxidation rates. In inorganic mixtures, a nitrate-to-chloride molar ratio of >1.5 accelerated photooxidation of azelaic acid indicating the dominant role of nitrate. Substantial inhibition effects of chloride on photooxidation of azelaic acid were demonstrated at a nitrate-to-chloride molar ratio <0.3. Nitrate and chloride are interrelated in affecting photooxidation of azelaic acid as photolysis of nitrate would significantly consume H +, retarding reaction of HOCl - with H +, and consequently decreasing rad OH-chloride reaction. pH affects photooxidation of C 2-C 9 dicarboxylic acids (DCAs) in two ways: C 2-C 4 dicarboxylates exhibit substantially higher degradation rates than their parent DCAs, while C 5-C 9 dicarboxylates demonstrate degradation rates similar to their parent DCAs.

Calcification resistance for photooxidatively crosslinked acellular bovine jugular vein conduits in right-side heart implantation.

PubMed

Lü, Wei-Dong; Wang, An-Ping; Wu, Zhong-Shi; Zhang, Ming; Hu, Tie-Hui; Lei, Guang-Yan; Hu, Ye-Rong

2012-10-01

This study aimed to investigate the effect of decellularization plus photooxidative crosslinking and ethanol pretreatment on bioprosthetic tissue calcification. Photooxidatively crosslinked acellular (PCA) bovine jugular vein conduits (BJVCs) and their photooxidized controls (n = 5 each) were sterilized in a graded concentration of ethanol solutions for 4 h, and used to reconstruct dog right ventricular outflow tracts. At 1-year implantation, echocardiography showed similar hemodynamic performance, but obvious calcification for the photooxidized BJVC walls. Further histological examination showed intense calcium deposition colocalized with slightly degraded elastic fibers in the photooxidized BJVC walls, with sparsely distributed punctate calcification in the valves and other areas of walls. But PCA BJVCs had apparent degradation of elastic fibers in the walls, with only sparsely distributed punctate calcification in the walls and valves. Content assay demonstrated comparable calcium content for the two groups at preimplantation, whereas less calcium for the PCA group in the walls and similar calcium in the valvular leaflets compared with the photooxidized group at 1-year retrieval. Elastin content assay presented the conduit walls of PCA group had less elastin content at preimplantation, but similar content at 1-year retrieval compared with the photooxidized group. Phospholipid analysis showed phospholipid extraction by ethanol for the PCA group was more efficacious than the photooxidized group. These results indicate that PCA BJVCs resist calcification in right-side heart implantation owing to decellularization, further photooxidative crosslinking, and subsequent phospholipid extraction by ethanol at preimplantation. Copyright © 2012 Wiley Periodicals, Inc.

The protective effect of salicylic acid on lysozyme against riboflavin-mediated photooxidation

NASA Astrophysics Data System (ADS)

Li, Kun; Wang, Hongbao; Cheng, Lingli; Zhu, Hui; Wang, Mei; Wang, Shi-Long

2011-06-01

As a metabolite of aspirin in vivo, salicylic acid was proved to protect lysozyme from riboflavin-mediated photooxidation in this study. The antioxidative properties of salicylic acid were further studied by using time-resolved laser flash photolysis of 355 nm. It can quench the triplet state of riboflavin via electron transfer from salicylic acid to the triplet state of riboflavin with a reaction constant of 2.25 × 10 9 M -1 s -1. Mechanism of antioxidant activities of salicylic acid on lysozyme oxidation was discussed. Salicylic acid can serve as a potential antioxidant to quench the triplet state of riboflavin and reduce oxidative pressure.

A model study of laboratory photooxidation experiments of mono- and sesquiterpenes

NASA Astrophysics Data System (ADS)

Capouet, M.; Vereecken, L.; Peeters, J.; Müller, J.

2006-12-01

The importance of monoterpenes in the atmosphere stems from their large emissions from plants, their high reactivity, and their role as precursors for Secondary Organic Aerosol (SOA) production. In order to quantify the impact of α-pinene oxidation (as representative of the monoterpenes) using a CTM, a detailed understanding of its oxidation mechanism is necessary. Past studies have investigated successfully the gas- phase OH-oxidation mechanism of α-pinene [Peeters et al., 2001; Vereecken and Peeters 2004; Capouet et al., 2004]. However, the SOA formation measured in laboratory experiments remains difficult to model, partly due to a poor understanding of the ozonolysis mechanism believed to be the dominant path to formation of condensable compounds. Very recently, Peeters and co-workers have developed a detailed mechanism for the α-pinene ozonolysis based on objective theoretical grounds. Both OH- and O3- oxidation mechanisms have been implemented in a box model and coupled to a module describing the gas/particle partitioning of the semi-volatile products on the basis of a vapour pressure prediction method [Capouet and Müller, 2006]. The photooxidation of primary products has been parameterized in order to evaluate the role of condensable compounds formed by secondary reactions. Simulations of a wide set of α-pinene photooxidation experiments reported in the literature have been performed. Results indicate that the calculated SOA contain a significant fraction of second generation products. Note in particular that our box model simulations as well as theoretical arguments contradict the gas-phase formation routes for pinic acid proposed in the literature and suggest a secondary origin for this compound. Contribution of the sesquiterpenes to biogenic non methane hydrocarbon emissions has been estimated from 9% to 28% in some regions in the U.S. Their high reactivity towards ozone and their complex chemistry make these compounds hardly accessible to theoretical and experimental study. Lately an increasing number of laboratory experiments have been performed and have reported that sesquiterpenes such as β- caryophyllene and α-humulene have much higher aerosol formation potentials than α-pinene on a mass basis. Using parameterizations similar to those developed previously for α-pinene, a simplified box model describing the oxidation of the sesquiterpenes and the related aerosol formation has been developed. Preliminary simulations of photooxidation experiments have been performed and are compared with the monoterpenes model results.

Perturbations of carotenoid and tetrapyrrole biosynthetic pathways result in differential alterations in chloroplast function and plastid signaling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Joon-Heum; Jung, Sunyo

In this study, we used the biosynthetic inhibitors of carotenoid and tetrapyrrole biosynthetic pathways, norflurazon (NF) and oxyfluorfen (OF), as tools to gain insight into mechanisms of photooxidation in rice plants. NF resulted in bleaching symptom on leaves of the treated plants, whereas OF treatment developed a fast symptom of an apparent necrotic phenotype. Both plants exhibited decreases in photosynthetic efficiency, as indicated by F{sub v}/F{sub m}. NF caused severe disruption in thylakoid membranes, whereas OF-treated plants exhibited disruption of chloroplast envelope and plasma membrane. Levels of Lhca and Lhcb proteins in photosystem I (PSI) and PSII were reduced bymore » photooxidative stress in NF- and OF-treated plants, with a greater decrease in NF plants. The down-regulation of nuclear-encoded photosynthesis genes Lhcb and rbcS was also found in both NF- and OF-treated plants, whereas plastid-encoded photosynthetic genes including RbcL, PsaC, and PsbD accumulated normally in NF plants but decreased drastically in OF plants. This proposes that the plastids in NF plants retain their potential to develop thylakoid membranes and that photobleaching is mainly controlled by nuclear genes. Distinct photooxidation patterns between NF- and OF-treated plants developed differential signaling, which might enable the plant to coordinate the expression of photosynthetic genes from the nuclear and plastidic genomes. - Highlights: • Two modes of photooxidation by carotenoid and tetrapyrrole biosynthetic inhibitors. • We examine differential alterations in chloroplast function and plastid signaling. • NF and OF cause differential alterations in chloroplast ultrastructure and function. • Photooxidation coordinates photosynthetic gene expression from nucleus and plastid.« less

Visible light-induced oxidation of unsaturated components of cutins: a significant process during the senescence of higher plants.

PubMed

Rontani, Jean-François; Rabourdin, Adélaïde; Pinot, Franck; Kandel, Sylvie; Aubert, Claude

2005-02-01

9-Hydroperoxy-18-hydroxyoctadec-10(trans)-enoic and 10-hydroperoxy-18-hydroxyoctadec-8(trans)-enoic acids deriving from type II (i.e. involving 1O2) photooxidation of 18-hydroxyoleic acid were detected after visible light-induced senescence experiments carried out with Petroselinum sativum and subsequent cutin depolymerisation. These results showed that in senescent plants, where the 1O2 formation rate exceeds the quenching capacity of the photoprotective system, 1O2 can migrate outside the chloroplasts and affect the unsaturated components of cutins. Significant amounts of 9,18-dihydroxyoctadec-10(trans)-enoic and 10,18-dihydroxyoctadec-8(trans)-enoic acids resulting from the reduction of these photoproducts of 18-hydroxyoleic acid were also detected in different natural samples. These results well support the significance of the photooxidation of the unsaturated components of higher plant cutins in the natural environment.

The Arabidopsis aba4-1 mutant reveals a specific function for neoxanthin in protection against photooxidative stress.

PubMed

Dall'Osto, Luca; Cazzaniga, Stefano; North, Helen; Marion-Poll, Annie; Bassi, Roberto

2007-03-01

The aba4-1 mutant completely lacks neoxanthin but retains all other xanthophyll species. The missing neoxanthin in light-harvesting complex (Lhc) proteins is compensated for by higher levels of violaxanthin, albeit with lower capacity for photoprotection compared with proteins with wild-type levels of neoxanthin. Detached leaves of aba4-1 were more sensitive to oxidative stress than the wild type when exposed to high light and incubated in a solution of photosensitizer agents. Both treatments caused more rapid pigment bleaching and lipid oxidation in aba4-1 than wild-type plants, suggesting that neoxanthin acts as an antioxidant within the photosystem II (PSII) supercomplex in thylakoids. While neoxanthin-depleted Lhc proteins and leaves had similar sensitivity as the wild type to hydrogen peroxide and singlet oxygen, they were more sensitive to superoxide anions. aba4-1 intact plants were not more sensitive than the wild type to high-light stress, indicating the existence of compensatory mechanisms of photoprotection involving the accumulation of zeaxanthin. However, the aba4-1 npq1 double mutant, lacking zeaxanthin and neoxanthin, underwent stronger PSII photoinhibition and more extensive oxidation of pigments than the npq1 mutant, which still contains neoxanthin. We conclude that neoxanthin preserves PSII from photoinactivation and protects membrane lipids from photooxidation by reactive oxygen species. Neoxanthin appears particularly active against superoxide anions produced by the Mehler's reaction, whose rate is known to be enhanced in abiotic stress conditions.

The Arabidopsis aba4-1 Mutant Reveals a Specific Function for Neoxanthin in Protection against Photooxidative Stress[W

PubMed Central

Dall'Osto, Luca; Cazzaniga, Stefano; North, Helen; Marion-Poll, Annie; Bassi, Roberto

2007-01-01

The aba4-1 mutant completely lacks neoxanthin but retains all other xanthophyll species. The missing neoxanthin in light-harvesting complex (Lhc) proteins is compensated for by higher levels of violaxanthin, albeit with lower capacity for photoprotection compared with proteins with wild-type levels of neoxanthin. Detached leaves of aba4-1 were more sensitive to oxidative stress than the wild type when exposed to high light and incubated in a solution of photosensitizer agents. Both treatments caused more rapid pigment bleaching and lipid oxidation in aba4-1 than wild-type plants, suggesting that neoxanthin acts as an antioxidant within the photosystem II (PSII) supercomplex in thylakoids. While neoxanthin-depleted Lhc proteins and leaves had similar sensitivity as the wild type to hydrogen peroxide and singlet oxygen, they were more sensitive to superoxide anions. aba4-1 intact plants were not more sensitive than the wild type to high-light stress, indicating the existence of compensatory mechanisms of photoprotection involving the accumulation of zeaxanthin. However, the aba4-1 npq1 double mutant, lacking zeaxanthin and neoxanthin, underwent stronger PSII photoinhibition and more extensive oxidation of pigments than the npq1 mutant, which still contains neoxanthin. We conclude that neoxanthin preserves PSII from photoinactivation and protects membrane lipids from photooxidation by reactive oxygen species. Neoxanthin appears particularly active against superoxide anions produced by the Mehler's reaction, whose rate is known to be enhanced in abiotic stress conditions. PMID:17351115

The molecular products and biogeochemical significance of lipid photooxidation in West Antarctic surface waters

NASA Astrophysics Data System (ADS)

Collins, James R.; Fredricks, Helen F.; Bowman, Jeff S.; Ward, Collin P.; Moreno, Carly; Longnecker, Krista; Marchetti, Adrian; Hansel, Colleen M.; Ducklow, Hugh W.; Van Mooy, Benjamin A. S.

2018-07-01

The seasonal depletion of stratospheric ozone over the Southern Hemisphere allows abnormally high doses of ultraviolet radiation (UVR) to reach surface waters of the West Antarctic Peninsula (WAP) in the austral spring, creating a natural laboratory for the study of lipid photooxidation in the shallow mixed layer of the marginal ice zone. The photooxidation of lipids under such conditions has been identified as a significant source of stress to microorganisms and short-chain fatty acids altered by photochemical processes have been found in both marine aerosols and sinking marine particle material. However, the biogeochemical impact of lipid photooxidation has not been quantitatively compared at ecosystem scale to the many other biological and abiotic processes that can transform particulate organic matter in the surface ocean. We combined results from field experiments with diverse environmental data, including high-resolution, accurate-mass HPLC-ESI-MS analysis of lipid extracts and in situ measurements of ultraviolet irradiance, to address several unresolved questions about lipid photooxidation in the marine environment. In our experiments, we used liposomes-nonliving, cell-like aggregations of lipids-to examine the photolability of various moieties of the intact polar diacylglycerol (IP-DAG) phosphatidylcholine (PC), a structural component of membranes in a broad range of microorganisms. We observed significant rates of photooxidation only when the molecule contained the polyunsaturated fatty acid (PUFA) docosahexaenoic acid (DHA). As the DHA-containing lipid was oxidized, we observed the steady ingrowth of a diversity of oxylipins and oxidized IP-DAG; our results suggest both the intact IP-DAG the degradation products were amenable to heterotrophic assimilation. To complement our experiments, we used an enhanced version of a new lipidomics discovery software package to identify the lipids in water column samples and in several diatom isolates. The galactolipid digalactosyldiacylglycerol (DGDG), the sulfolipid sulfoquinovosyldiacylglycerol (SQDG) and the phospholipids PC and phosphatidylglycerol (PG) accounted for the majority of IP-DAG in the water column particulate (≥0.2 μm) size fraction; between 3.4 and 5.3% of the IP-DAG contained fatty acids that were both highly polyunsaturated (i.e., each containing ≥5 double bonds). Using a broadband apparent quantum yield (AQY) that accounted for direct and Type I (i.e., radical-mediated) photooxidation of PUFA-containing IP-DAG, we estimated that 0.7 ± 0.2 μmol IP-DAG m-2 d-1 (0.5 ± 0.1 mg C m-2 d-1) were oxidized by photochemical processes in the mixed layer. This rate represented 4.4% (range, 3-21%) of the mean bacterial production rate measured in the same waters immediately following the retreat of the sea ice. Because our liposome experiments were not designed to account for oxidation by Type II photosensitized processes that often dominate in marine phytodetritus, our rate estimates may represent a sizeable underestimate of the true rate of lipid photooxidation in the water column. While production of such diverse oxidized lipids and oxylipins has been previously observed in terrestrial plants and mammals in response to biological stressors such as disease, we show here that a similar suite of molecules can be produced via an abiotic process in the environment and that the effect can be commensurate in magnitude with other ecosystem-scale biogeochemical processes.

Chemiluminescence and reactivity of the composites based on blends of polypropylene and polyamide

NASA Astrophysics Data System (ADS)

Vorontsov, N. V.; Popov, A. A.; Margolin, A. L.

2017-12-01

The effect of the composition of blends based on isotactic polypropylene (PP) and aliphatic polyamide 6/66-4 (PA) on the rate of photo-oxidation of their mixtures in air at room temperature has been studied. The decay of photoinduced chemiluminescence was studied to determine the kinetics of peroxyl radical termination in composites and the rate constants of this process depending on the composition of the mixtures. In the presence of PA, the rate of photo-oxidation of mixtures is much higher than the rates of photo-oxidation of separately taken components, PP and PA. Thus, the kinetics of photo-oxidation of mixtures differs from the simple sum of photo-oxidation kinetics of PP and PA, which should be expected in the absence of chemical and physical interaction of the components of the mixture. A decrease in the rate constants due to PA additives indicates a decrease in the mobility of molecules in the composites and explains the observed increase in photo-oxidation of mixtures.

ESR Analysis of Polymer Photo-Oxidation

NASA Technical Reports Server (NTRS)

Kim, Soon Sam; Liang, Ranty Hing; Tsay, Fun-Dow; Gupta, Amitave

1987-01-01

Electron-spin resonance identifies polymer-degradation reactions and their kinetics. New technique enables derivation of kinetic model of specific chemical reactions involved in degradation of particular polymer. Detailed information provided by new method enables prediction of aging characteristics long before manifestation of macroscopic mechanical properties.

Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

PubMed

Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

2012-06-21

The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

Atmospheric hydrogen peroxide and Eoarchean iron formations.

PubMed

Pecoits, E; Smith, M L; Catling, D C; Philippot, P; Kappler, A; Konhauser, K O

2015-01-01

It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earth's oldest IF. © 2014 John Wiley & Sons Ltd.

Transcriptional and posttranscriptional regulation of the glycolate oxidase gene in tobacco seedlings.

PubMed

Barak, S; Nejidat, A; Heimer, Y; Volokita, M

2001-03-01

The roles of light and of the putative plastid signal in glycolate oxidase (GLO) gene expression were investigated in tobacco (Nicotiana tabacum cv. Samsun NN) seedlings during their shift from skotomorphogenic to photomorphogenic development. GLO transcript and enzyme activities were detected in etiolated seedlings. Their respective levels increased three- and six-fold during 96 h of exposure to light. The GLO transcript was almost undetectable in seedlings in which chloroplast development was impaired by photooxidation with the herbicide norflurazon. In transgenic tobacco seedlings, photooxidation inhibited the light-dependent increase in GUS activity when it was placed under the regulation of the GLO promoter P(GLO). However, even under these photooxidative conditions, a continuous increase in GUS activity was observed as compared to etiolated seedlings. When GUS expression was driven by the CaMV 35S promoter (P35S), no apparent difference was observed between etiolated, deetiolated and photooxidized seedlings. These observations indicate that the effects of the putative plastid development signal and light on GUS expression can be separated. Translational yield analysis indicated that the translation of the GUS transcript in P(GLO)::GUS seedlings was enhanced 30-fold over that of the GUS transcript in P35S::GUS seedlings. The overall picture emerging from these results is that in etiolated seedlings GLO transcript, though present at a substantial level, is translated at a low rate. Increased GLO transcription is enhanced, however, in response to signals originating from the developing plastids. GLO gene expression is further enhanced at the translational level by a yet undefined light-dependent mechanism.

Light-Induced Acclimation of the Arabidopsis chlorina1 Mutant to Singlet Oxygen[C][W

PubMed Central

Ramel, Fanny; Ksas, Brigitte; Akkari, Elsy; Mialoundama, Alexis S.; Monnet, Fabien; Krieger-Liszkay, Anja; Ravanat, Jean-Luc; Mueller, Martin J.; Bouvier, Florence; Havaux, Michel

2013-01-01

Singlet oxygen (1O2) is a reactive oxygen species that can function as a stress signal in plant leaves leading to programmed cell death. In microalgae, 1O2-induced transcriptomic changes result in acclimation to 1O2. Here, using a chlorophyll b–less Arabidopsis thaliana mutant (chlorina1 [ch1]), we show that this phenomenon can also occur in vascular plants. The ch1 mutant is highly photosensitive due to a selective increase in the release of 1O2 by photosystem II. Under photooxidative stress conditions, the gene expression profile of ch1 mutant leaves very much resembled the gene responses to 1O2 reported in the Arabidopsis mutant flu. Preexposure of ch1 plants to moderately elevated light intensities eliminated photooxidative damage without suppressing 1O2 formation, indicating acclimation to 1O2. Substantial differences in gene expression were observed between acclimation and high-light stress: A number of transcription factors were selectively induced by acclimation, and contrasting effects were observed for the jasmonate pathway. Jasmonate biosynthesis was strongly induced in ch1 mutant plants under high-light stress and was noticeably repressed under acclimation conditions, suggesting the involvement of this hormone in 1O2-induced cell death. This was confirmed by the decreased tolerance to photooxidative damage of jasmonate-treated ch1 plants and by the increased tolerance of the jasmonate-deficient mutant delayed-dehiscence2. PMID:23590883

A COMPARISON OF LIQUID AND GAS-PHASE PHOTOOXIDATION TREATMENT OF METHYL TERTIARY BUTYL ETHER: SYNTHETIC AND FIELD SAMPLES

EPA Science Inventory

The feasibility of photo-oxidation treatment of metyl tert-butyl either (MTBE) in water was investigated using two systems, 1) a slurry falling film photo-reactor, and 2) an integrated air-stripping with gas phase photooxidation system. MTBE-contaminated synthetic water and field...

Photochemical stability of UV-screening transparent acrylic copolymers of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole

NASA Technical Reports Server (NTRS)

Gupta, A.; Scott, G. W.; Kliger, D.; Vogl, O.

1983-01-01

The mechanism of photodegradation of certain hydroxyphenyl benzotriazole based ultraviolet absorbers has been investigated and a new polymerizable ultraviolet absorber in this group has been synthesized. The photoreactivity is entirely confined at the surface of polymethylmethacrylate films containing the ultraviolet absorbers as pendant groups. A mechanism involving sensitized photooxidation has been proposed to interpret the data.

Modelling of polymer photodegradation for solar cell modules

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1981-01-01

A computer model including an integration routine was developed and demonstrated to simulate, in principle, the chemical changes which may occur in the photooxidation of hydrocarbons, using as input data a set of elementary reactions, corresponding rate constants and appropriate starting conditions. Application of this model to the photooxidation of pottant and plastic materials used in the LSA module designs provides a reliable predictive capability regarding the useful lifetime of these materials. An earlier mechanism consisting of 46 reactions was simplified considerably by reducing the number of formal termination steps since it became apparent that the major termination process goes via the peroxy radicals. In addition, new reactions of oxygen with acryl radicals (from Norrish type I) to form peracids, which then decompose to form carbon dioxide are included.

Potential role of CS2 photooxidation in tropospheric sulfur chemistry

NASA Technical Reports Server (NTRS)

Wine, P. H.; Chameides, W. L.; Ravishankara, A. R.

1981-01-01

Absorption cross section measurements and model calculations indicate that CS2 photooxidation may be an important tropospheric sink for the CS2, giving a lifetime on the order of a week or two. If background CS2 levels are 10-20 pptv, then CS2 photooxidation may be an important global source of OCS as well.

Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, Heinz; Blatter, Fritz; Sun, Hai

1999-01-01

A process for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

Photooxidation of Alpha-Pinene at High Relative Humidity in the Presence of Increasing Concentrations of NOx

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Yong; Ezell, Michael J.; Zelenyuk, Alla

2008-06-01

The photooxidation of ~1 ppm alpha-pinene in the presence of increasing concentrations of NO2 was studied in a Teflon chamber at relative humidities from 70 - 88% and temperatures from 296 - 304 K. The loss of alpha-pinene and formation of gas phase products were followed using proton transfer reaction mass spectrometry (PTR-MS). Gas phase reaction products measured by PTR-MS and their yields include formaldehyde (5 + 1%), formic acid (2.5 + 1.4%), methanol (0.6 + 0.3%), acetaldehyde (3.9 + 1.7%), acetic acid (10 + 2%), acetone (11.5 + 3.1%), pinonaldehyde (22 + 6%), and pinene oxide (0.9 + 0.1%).more » There was evidence of organic nitrates in the gas phase and small peaks were tentatively assigned to norpinonaldehyde, 4-oxopinonaldehyde, propanedial, 2,3-dioxobutanal and 3,5,6-trioxoheptanal or 3-hydroxymethyl-2,2-dimethylcyclobutylethanone. The formation and growth of new particles were followed using a scanning mobility particle sizer (SMPS), and their chemical composition was probed using single particle mass spectrometry (SPLAT II). SPLAT II analysis also provided measurements of the vacuum aerodynamic diameters of the newly formed secondary organic aerosol (SOA) particles and, in combination with the electrical mobility diameter, a particle density of 1.21 + 0.02 g cm-3 was calculated, 20% larger than often assumed in calculating SOA yields. SPLAT II showed that the suspended SOA consisted of a complex mixture of organic nitrates and organics, possibly including pinonic acid, pinic acid and trans-sobrerol. Three-wavelength light scattering measurements made using an integrating nephelometer were consistent with particles having a refractive index characteristic of organic compounds, but the data could not be well matched at all three wavelengths with a single refractive index. The effect of addition of cyclohexane or NO on particle formation showed that ozonolysis was the major mechanism of SOA formation in this system. However, unlike simple ozonolysis, organic nitrates are formed in both the gas and particle phases. Identifying and measuring specific organic nitrates in both the gas and particle phases in air may help to elucidate why SOA formation has been reported in field studies to be associated with polluted urban areas, yet the carbon in these particles is largely contemporary, i.e., non-fossil fuel carbon.« less

Photooxidation of Trimethyl Phosphite in Nitrogen, Oxygen, and para-Hydrogen Matrixes at Low Temperatures.

PubMed

Ramanathan, N; Sundararajan, K; Gopi, R; Sankaran, K

2017-03-16

Trimethyl phosphite (TMPhite) was photooxidized to trimethyl phosphate (TMP) in N 2 , O 2 , and para-H 2 matrixes at low temperatures to correlate the conformational landscape of these two molecules. The photooxidation produced the trans (TGG)-rich conformer with respect to the ground state gauche (GGG) conformer of TMP in N 2 and O 2 matrixes, which has diverged from the conformational composition of freshly deposited pure TMP in the low-temperature matrixes. The enrichment of the trans conformer in preference to the gauche conformer of TMP during photooxidation is due to the TMPhite precursor, which exists exclusively in the trans conformer. Interestingly, whereas the photooxidized TMP molecule suffers site effects possibly due to the local asymmetry in N 2 and O 2 matrixes, in the para-H 2 matrix owing to the quantum crystal nature the site effects were observed to be self-repaired.

Epoxide as a Precursor to Secondary Organic Aerosol Formation from Isoprene Photooxidation in the Presence of Nitrogen Oxides

EPA Science Inventory

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear...

Oligomers Formed Through In-cloud Metylglyoxal Reactions: Chemical Composition, Properties, and Mechanisms Investigated by Ultra-high Resolution FT-ICR Mass Spectrometry

EPA Science Inventory

Secondary organic aerosol (SOA) is a substantial component of total atmospheric organic particulate matter, but little is known about the composition of SOA formed through cloud processing. We conducted aqueous phase photooxidation experiments of methylglyoxal and hydroxyl radica...

Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, H.; Blatter, F.; Sun, H.

1999-06-22

A process is described for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts. 19 figs.

Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, Heinz; Blatter, Fritz; Sun, Hai

2001-01-01

A process for a combined selective thermal oxidation and photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly combined selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

Photoinduced oxidation of a water-soluble manganese(III) porphyrin

PubMed Central

Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

1986-01-01

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly. PMID:16593699

Monitoring of TiO2-catalytic UV-LED photo-oxidation of cyanide contained in mine wastewater and leachate.

PubMed

Kim, Seong Hee; Lee, Sang Woo; Lee, Gye Min; Lee, Byung-Tae; Yun, Seong-Taek; Kim, Soon-Oh

2016-01-01

A photo-oxidation process using UV-LEDs and TiO2 was studied for removal of cyanide contained in mine wastewater and leachates. This study focused on monitoring of a TiO2-catalyzed LED photo-oxidation process, particularly emphasizing the effects of TiO2 form and light source on the efficiency of cyanide removal. The generation of hydroxyl radicals was also examined during the process to evaluate the mechanism of the photo-catalytic process. The apparent removal efficiency of UV-LEDs was lower than that achieved using a UV-lamp, but cyanide removal in response to irradiation as well as consumption of electrical energy was observed to be higher for UV-LEDs than for UV-lamps. The Degussa P25 TiO2 showed the highest performance of the TiO2 photo-catalysts tested. The experimental results indicate that hydroxyl radicals oxidize cyanide to OCN(-), NO2(-), NO3(-), HCO3(-), and CO3(2-), which have lower toxicity than cyanide. In addition, the overall efficacy of the process appeared to be significantly affected by diverse operational parameters, such as the mixing ratio of anatase and rutile, the type of gas injected, and the number of UV-LEDs used. Copyright © 2015 Elsevier Ltd. All rights reserved.

DELLAs Regulate Chlorophyll and Carotenoid Biosynthesis to Prevent Photooxidative Damage during Seedling Deetiolation in Arabidopsis[C][W

PubMed Central

Cheminant, Soizic; Wild, Michael; Bouvier, Florence; Pelletier, Sandra; Renou, Jean-Pierre; Erhardt, Mathieu; Hayes, Scott; Terry, Matthew J.; Genschik, Pascal; Achard, Patrick

2011-01-01

In plants, light represents an important environmental signal that triggers the production of photosynthetically active chloroplasts. This developmental switch is critical for plant survival because chlorophyll precursors that accumulate in darkness can be extremely destructive when illuminated. Thus, plants have evolved mechanisms to adaptively control plastid development during the transition into light. Here, we report that the gibberellin (GA)-regulated DELLA proteins play a crucial role in the formation of functional chloroplasts during deetiolation. We show that Arabidopsis thaliana DELLAs accumulating in etiolated cotyledons derepress chlorophyll and carotenoid biosynthetic pathways in the dark by repressing the transcriptional activity of the phytochrome-interacting factor proteins. Accordingly, dark-grown GA-deficient ga1-3 mutants (that accumulate DELLAs) display a similar gene expression pattern to wild-type seedlings grown in the light. Consistent with this, ga1-3 seedlings accumulate higher amounts of protochlorophyllide (a phototoxic chlorophyll precursor) in darkness but, surprisingly, are substantially more resistant to photooxidative damage following transfer into light. This is due to the DELLA-dependent upregulation of the photoprotective enzyme protochlorophyllide oxidoreductase (POR) in the dark. Our results emphasize the role of DELLAs in regulating the levels of POR, protochlorophyllide, and carotenoids in the dark and in protecting etiolated seedlings against photooxidative damage during initial light exposure. PMID:21571951

Photo-oxidation of LDPE: Effects on elongational viscosity

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor H.; Wagner, Manfred H.

2013-04-01

Sheets of low-density polyethylene (LDPE) were photo-oxidatively treated at room temperature, and subsequently characterized rheologically in the melt state by shear and uniaxial extensional experiments. For photo-oxidation, a xenon lamp was used to irradiate the samples for times between 1 day and 6 weeks. Linear-viscoelastic characterization was performed in a temperature range of 130 to 220°C to obtain the master curve at 170°C, the reference temperature at which the elongational viscosities were measured. Linear viscoelasticity is increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by an increasing gel fraction as determined by a solvent extraction method. The elongational measurements reveal a strong enhancement of strain hardening until a saturation level is achieved. The elongational data are analyzed in the frame work of two constitutive equations, the rubber-like liquid and the molecular stress function models. Within the experimental window, time-deformation separability is confirmed for all samples, independent of the degree of photo-oxidation.

Elongational viscosity of photo-oxidated LDPE

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor H.; Wagner, Manfred H.

2014-05-01

Sheets of low-density polyethylene (LDPE) were photo-oxidatively treated at room temperature, and subsequently characterized rheologically in the melt state by shear and uniaxial extensional experiments. For photo-oxidation, a xenon lamp was used to irradiate the samples for times between 1 day and 6 weeks. Linear-viscoelastic characterization was performed in a temperature range of 130 to 220°C to obtain the master curve at 170°C, the reference temperature at which the elongational viscosities were measured. Linear viscoelasticity is increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by an increasing gel fraction as determined by a solvent extraction method. The elongational measurements reveal a strong enhancement of strain hardening until a saturation level is achieved. The elongational data are analyzed in the frame work of two constitutive equations, the rubber-like liquid and the molecular stress function models. Within the experimental window, timedeformation separability is confirmed for all samples, independent of the degree of photo-oxidation.

A Novel Inlet System for On-line Chemical Analysis of Semi-Volatile Submicron Particulate Matter

NASA Astrophysics Data System (ADS)

Wisthaler, A.; Eichler, P.; Müller, M.

2015-12-01

Semi-volatile organic molecules bound to particles are difficult to measure, especially if they are reactive in nature. Any technique based on aerosol collection onto a substrate generates sampling artifacts due to surface reactions and ad- and desorption of semi-volatile analytes. On-line sampling without sample pre-collection, as for example implemented in the AMS, has greatly reduced many sampling artifacts. AMS measurements of organics do, however, suffer from the drawback that molecular-level information is, in most cases, lost during hard ionization events. As a consequence, only little speciated and thus mechanistically informative data on organic matter is obtained. PTR-ToF-MS is a well-established on-line measurement technique for gas-phase organics. Soft ionization via gas-phase hydronium ions preserves, to a large extent, molecular-level information and thus allows identifying organic compounds at an elemental composition level. We have recently developed a particle inlet system for PTR-ToF-MS instruments (doi:10.5194/amt-8-1353-2015). The CHARON ("Chemical Analysis of Aerosol On-line") inlet consists of a gas-phase denuder, an aerodynamic lens and a thermodesorption unit. In its latest version, it includes a heatable tube upstream of the denuder to form a thermodenuder. Over the last year, the CHARON PTR-ToF-MS system has been successfully used in a series of measurement campaigns to characterize i) POA emitted from a marine diesel engine, ii) SOA generated from the photo-oxidation of toluene, iii) SOA generated from the photo-oxidation of selected amines, iv) ambient aerosol in two major European cities and v) SOA generated from the photo-oxidation of biogenic VOCs. These measurements have demonstrated that the CHARON PTR-ToF-MS system i) generates on-line and real-time elemental composition information of semi-volatile organics in submicron particles (both POA and SOA), ii) detects 80-100 % of the organic mass as measured by the AMS and iii) generates volatility information of semi-volatile organics at an elemental composition level. Selected application examples will be shown.

Biodegradation of photo-oxidized lignite and characterization of the products

NASA Astrophysics Data System (ADS)

Li, Jiantao; Liu, Xiangrong; Yue, Zilin; Zhang, Yaowen

2018-01-01

Biodegradation of photo-oxidized Inner Mongolia lignite by pseudomonas aeruginosa was studied and the degradation percentage reached 56.27%, while the corresponding degradation percentage of the strain degrading raw Inner Mongolia lignite is only 23.16%. The degradation products were characterized. Proximate and ultimate analyses show that the higher oxygen content increased by photo-oxidation pretreatment maybe promoted the degradation process. Ultraviolet spectroscopy (UV) analysis of the liquid product reveals that it contains unsaturated structures and aromatic rings are the main structure units. Gas chromatography-mass spectrometry (GC-MS) analysis indicates that the main components of the ethyl acetate extracts are low molecular weight organic compounds, such as ketones, acids, hydrocarbons, esters and alcohols. Infrared spectroscopy (IR) analysis of raw lignite, photo-oxidized lignite and residual lignite demonstrates that the absorption peaks of functional groups in residual lignite disappeared or weakened obviously. Scanning electron microscopy (SEM) analysis manifests that small holes appear in photo-oxidized lignite surface, which may be promote the degradation process and this is only from the physical morphology aspects, so it can be inferred from the tests and analyses results that the more important reason of the high degradation percentage is mostly that the photo-oxidation pretreatment changes the chemical structures of lignite.

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1982-01-01

A computer model which simulates, in principle, the chemical changes in the photooxidation of hydrocarbons using as input data a set of elementary reactions, corresponding kinetic rate data and appropriate initial conditions was developed. The Model was refined and exploited to examine more closely the photooxidation and photostabilization of a hydrocarbon polymer. The results lead to the following observations. (1) The time to failure, tau sub f (chosen as the level of 5% C-H bond oxidation which is within the range anticipated for marked change in mechanical properties) varies as the inverse square root of the light intensity. However, tau sub f is almost unaffected by both the photoinitiator type and concentration. (2) The time to failure decreases with the rate of abstraction of C-H by peroxy radicals but increases with the rate of bimolecular radical termination controlled by diffusion. (3) Of the various stabilization mechanisms considered, the trapping of peroxy radicals is distinctly the most effective, although the concommitant decomposition of hydroperoxide is also desirable.

Quenching of triplet-excited flavins by flavonoids. Structural assessment of antioxidative activity.

PubMed

Huvaere, Kevin; Olsen, Karsten; Skibsted, Leif H

2009-10-02

The mechanism of flavin-mediated photooxidation of flavonoids was investigated for aqueous solutions. Interaction of triplet-excited flavin mononucleotide with phenols, as determined by laser flash photolysis, occurred at nearly diffusion-controlled rates (k approximately 1.6 x 10(9) L mol(-1) s(-1) for phenol at pH 7, 293 K), but protection of the phenolic function by methylation inhibited reaction. Still, electron transfer was proposed as the dominating mechanism due to the lack of primary kinetic hydrogen/deuterium isotope effect and the low activation enthalpy (<20 kJ mol(-1)) for photooxidation. Activation entropy worked compensating in a series of phenolic derivatives, supporting a common oxidation mechanism. An ortho-hydroxymethoxy pattern was equally reactive (k approximately 2.3 x 10(9) L mol(-1) s(-1) for guaiacol at pH 7) as compounds with ortho-dihydroxy substitution (k approximately 2.4 x 10(9) L mol(-1) s(-1) for catechol at pH 7), which are generally referred to as good antioxidants. This refutes the common belief that stabilization of incipient phenoxyl radicals through intramolecular hydrogen bonding is the driving force behind the reducing activity of catechol-like compounds. Instead, such bonding improves ionization characteristics of the substrates, hence the differences in reactivity with (photo)oxidation of isolated phenols. Despite the similar reactivity, radicals from ortho-dihydroxy compounds are detected in high steady-state concentrations by electron paramagnetic resonance (EPR) spectroscopy, while those resulting from oxidation of ortho-hydroxymethoxy (or isolated phenolic) patterns were too reactive to be observed. The ability to deprotonate and form the corresponding radical anions at neutral pH was proposed as the decisive factor for stabilization and, consequently, for antioxidative action. Thus, substituting other ionizable functions for the ortho- or para-hydroxyl in phenolic compounds resulted in stable radical anion formation, as demonstrated for para-hydroxybenzoic acid, in contrast to its methyl ester.

Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination

DOE PAGES

Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; ...

2015-11-10

Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (λ > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.

Characterization of secondary organic aerosol from photo-oxidation of gasoline exhaust and specific sources of major components.

PubMed

Ma, Pengkun; Zhang, Peng; Shu, Jinian; Yang, Bo; Zhang, Haixu

2018-01-01

To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C 7 -C 9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1983-01-01

A computer model was developed which can generate realistic concentration versus time profiles of the chemical species formed during photooxidation of hydrocarbon polymers using as input data a set of elementary reactions with corresponding rate constants and initial conditions. The results of computer simulation have been shown to be consistent with the general experimental observations of the photooxidation of polyethylene exposed to sunlight at ambient temperatures. The useful lifetime (5% oxidation) of the unstabilized polyethylene is predicted to vary from a few months in hot weather (100 F) to almost two years in cool weather (45 F) with an apparent net activation energy of 10 kcal/mol. Modelling studies of alternate mechanisms for stabilization of clear, amorphous, linear polyethylene suggest that the optimum stabilizer would be a molecularly dispensed additive in very low concentration which can trap peroxy radicals and also decompose hydroperoxides.

Differentiating the roles of photooxidation and biodegradation in the weathering of Light Louisiana Sweet crude oil in surface water from the Deepwater Horizon site.

PubMed

Bacosa, Hernando P; Erdner, Deana L; Liu, Zhanfei

2015-06-15

We determined the contributions of photooxidation and biodegradation to the weathering of Light Louisiana Sweet crude oil by incubating surface water from the Deepwater Horizon site under natural sunlight and temperature conditions. N-alkane biodegradation rate constants were ca. ten-fold higher than the photooxidation rate constants. For the 2-3 ring and 4-5 ring polycyclic aromatic hydrocarbons (PAHs), photooxidation rate constants were 0.08-0.98day(-1) and 0.01-0.07day(-1), respectively. The dispersant Corexit enhanced degradation of n-alkanes but not of PAHs. Compared to biodegradation, photooxidation increased transformation of 4-5 ring PAHs by 70% and 3-4 ring alkylated PAHs by 36%. For the first time we observed that sunlight inhibited biodegradation of pristane and phytane, possibly due to inhibition of the bacteria that can degrade branched-alkanes. This study provides quantitative measures of oil degradation under relevant field conditions crucial for understanding and modeling the fate of spilled oil in the northern Gulf of Mexico. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

NASA Technical Reports Server (NTRS)

Formenti, M.; Juillet, F.; Teichner, S. J.

1977-01-01

Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase.

Photooxidation of Methionine

ERIC Educational Resources Information Center

Lewis, Catherine; Scouten, William H.

1976-01-01

Describes an experiment in which the photooxidation of methionine using free methylene blue as the sensitizer is applied to the isolated amino acid or to the methionyl residues of a complex polypeptide. (MLH)

Light and oxygenic photosynthesis: energy dissipation as a protection mechanism against photo-oxidation

PubMed Central

Szabó, Ildikó; Bergantino, Elisabetta; Giacometti, Giorgio Mario

2005-01-01

Efficient photosynthesis is of fundamental importance for plant survival and fitness. However, in oxygenic photosynthesis, the complex apparatus responsible for the conversion of light into chemical energy is susceptible to photodamage. Oxygenic photosynthetic organisms have therefore evolved several protective mechanisms to deal with light energy. Rapidly inducible non-photochemical quenching (NPQ) is a short-term response by which plants and eukaryotic algae dissipate excitation energy as heat. This review focuses on recent advances in the elucidation of the molecular mechanisms underlying this protective quenching pathway in higher plants. PMID:15995679

Perturbations of carotenoid and tetrapyrrole biosynthetic pathways result in differential alterations in chloroplast function and plastid signaling.

PubMed

Park, Joon-Heum; Jung, Sunyo

2017-01-22

In this study, we used the biosynthetic inhibitors of carotenoid and tetrapyrrole biosynthetic pathways, norflurazon (NF) and oxyfluorfen (OF), as tools to gain insight into mechanisms of photooxidation in rice plants. NF resulted in bleaching symptom on leaves of the treated plants, whereas OF treatment developed a fast symptom of an apparent necrotic phenotype. Both plants exhibited decreases in photosynthetic efficiency, as indicated by F v /F m . NF caused severe disruption in thylakoid membranes, whereas OF-treated plants exhibited disruption of chloroplast envelope and plasma membrane. Levels of Lhca and Lhcb proteins in photosystem I (PSI) and PSII were reduced by photooxidative stress in NF- and OF-treated plants, with a greater decrease in NF plants. The down-regulation of nuclear-encoded photosynthesis genes Lhcb and rbcS was also found in both NF- and OF-treated plants, whereas plastid-encoded photosynthetic genes including RbcL, PsaC, and PsbD accumulated normally in NF plants but decreased drastically in OF plants. This proposes that the plastids in NF plants retain their potential to develop thylakoid membranes and that photobleaching is mainly controlled by nuclear genes. Distinct photooxidation patterns between NF- and OF-treated plants developed differential signaling, which might enable the plant to coordinate the expression of photosynthetic genes from the nuclear and plastidic genomes. Copyright © 2016 Elsevier Inc. All rights reserved.

Sensitized photooxidation of phenols by fulvic acid and in natural waters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Faust, B.C.; Hoigne, J.

1987-10-01

In addition to singlet oxygen, irradiation of fulvic acid solutions and lake water with UV and visible light (lambda > 315 nm) produces another transient oxidant species. This transient oxidant (probably an organic peroxy radical) is derived from natural dissolved organic material (DOM) and controls DOM-sensitized photooxidations of various alkylphenols. On the basis of kinetic data for the transient oxidant, DOM-sensitized photooxidation half-lives of alkylphenols are estimated to range from 1 day to several months in middle-latitude shallow surface waters.

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

NASA Astrophysics Data System (ADS)

Sedlak, David L.; Hoigné, Jürg

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO 2) and superoxide (O 2-) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO 2/O 2-. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO 2/O 2-, and cycled between the Cu(II) and Cu(I) forms. Cu + reacted with FeOH 2+ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10 7 M -1s -1. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO 2/O 2-. Only at high oxalate concentrations was the Fe(II)C 2O 4 complex also formed, and it reacted relatively rapidly with hydrogen peroxide ( k = (3.1 ± 0.6) × 10 4 M -1s -1). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH 2+ with Cu(I) and HO 2/O 2-, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO 2 present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO 2/O 2-, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO 2/O 2-.

Fractionation of mercury isotopes by photo-oxidation in aquatic systems

NASA Astrophysics Data System (ADS)

Ghosh, S.; Bergquist, B. A.; Blum, J. D.

2009-12-01

Mercury is a globally distributed pollutant that bioaccumulates in aquatic food webs, even in remote locations. The recent discovery of both large mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) has made the promise of tracing this neurotoxin through the environment by using its isotopes very exciting. So far, the only process demonstrated experimentally to produce large MIF for Hg (similar in magnitude to the MIF observed in natural samples such as fish) is photochemical reduction (Bergquist and Blum, 2007). During photo-reduction, MIF of the odd isotopes was observed with the odd isotopes (199Hg, 201Hg) being preferentially enriched in the aqueous phase. Bergquist and Blum, 2007, suggested that the cause of MIF was the magnetic isotope effect (MIE), which is purely a kinetic phenomenon involving radical pair intermediates. Radical pairs with odd isotopes, which have non-zero nuclear spin and magnetic moments, can undergo spin conversion faster than radical pairs with non-magnetic even isotopes. This allows the odd and even isotopes to be preferentially enriched in different reaction products. MIE is a complex phenomenon that is dependent on several factors including hyperfine coupling, life-time of the radical pair, coupling strength of the radical pair, spin-orbital coupling, diffusion factors, and the solvent cage (space) in which the reaction occurs. Only under rare circumstances will all the factors be suitable for the expression of MIE in natural reactions. The goal of this study was to conduct aqueous photo-oxidation reactions to investigate whether this redox pathway expresses MIF (in the form of MIE) similar to the photo-reduction pathway. In natural systems, net photo-reduction of Hg (II) species results in the release of Hg(0) vapor to the atmosphere. However this net photo-reduction is a combination of both photo-reduction and photo-oxidation. In their experiments, Bergquist and Blum 2007, only investigated the aqueous photo-reduction pathway and suppressed the photo-oxidation reaction. Photochemical oxidation experiments of Hg(0) were performed in quartz reaction chambers using natural sunlight. Solutions of aqueous Hg(0) were prepared by continuously bubbling vapor Hg(0) generated by a gas-liquid separator into the quartz reaction chamber filled with water. Experiments were conducted in the presence of Cl- and other potential oxidants such as semiquinone, hydroxyl radicals and H2O2 to assess if the presence of these different oxidants showed significant differences in the expression of Hg isotopic fractionation during the photo-oxidation process. For experiments run in the presence of Cl- only, ~2% of Hg was oxidized at the end of 7 hours whereas in the presence of both semiquinone radical and Cl- , approximately 20% of Hg was oxidized at the end of 6 hours. In the experiment with hydroxyl radicals present, ~ 7% of Hg was oxidized at the end of 6.5 hours. Another set of experiments were conducted where the net photo-reduction was mimicked, which allowed both photo-oxidation and photo-reduction to occur. Isotopic results and their implications on the redox cycle of mercury obtained from these experiments will be discussed in detail.

Electron Transfer Activity of a de Novo Designed Copper Center in a Three-Helix Bundle Fold

PubMed Central

Plegaria, Jefferson S.; Herrero, Christian; Quaranta, Annamaria; Pecoraro, Vincent L.

2017-01-01

In this work, we characterized the intermolecular ET property of a de novo designed metallopeptide using laser-flash photolysis. α3D-CH3 is three-helix bundle peptide that was designed to contain a copper ET site found in the β-barrel fold of native cupredoxins. The ET activity of Cuα3D-CH3 was determined using five different photosensitizers. By exhibiting a complete depletion of the photo-oxidant and the successive formation of a Cu(II) species at 400 nm, the transient and generated spectra demonstrated an ET transfer reaction between the photo-oxidant and Cu(I)α3D-CH3. This observation illustrated our success in integrating an ET center within a de novo designed scaffold. From the kinetic traces at 400 nm, first-order and bimolecular rate constants of 105 s−1 and 108 M−1 s−1 were derived. Moreover, a Marcus equation analysis on the rate versus driving force study produced a reorganization energy of 1.1 eV, demonstrating that the helical fold of α3D requires further structural optimization to efficiently perform ET. PMID:26427552

Surface chemistry changes and microstructure evaluation of low density nanocluster polyethylene under natural weathering: A spectroscopic investigation

NASA Astrophysics Data System (ADS)

Hamzah, M.; Khenfouch, M.; Rjeb, A.; Sayouri, S.; Houssaini, D. S.; Darhouri, M.; Srinivasu, VV

2018-03-01

Polyethylene is the most commonly used plastic in daily life, covering wide areas of application e.g. this polymer is used as a greenhouses covering material. This article investigates the effect of photo-oxidation on commercial unstabilised Low Density Polyethylene (uLDPE), as result of outdoor weathering factors. In this study, the samples were exposed for four months to the natural weather. The physico-chemical effects of natural ageing were studied by attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopy to elucidate the chemical composition, the nature of chemical bonds established and further to interrogate the changes that occur on the surface of the uLDPE samples. The main chemical change of uLDPE results in the formation of different kinds of carbonyl and vinyl groups identifiable in the ATR-FTIR and XPS spectra. The degree of crystallinity for these samples was calculated in terms of time exposure. An increase in the degree of crystallinity due to chemicrystallization was observed, which we indicative of the occurrences of chain scission. During outdoor exposure it was found that the photo-oxidation results in the formation of chain scission occurrences via Norrish type II reactions.

Photooxidation products of polycyclic aromatic compounds containing sulfur.

PubMed

Bobinger, Stefan; Andersson, Jan T

2009-11-01

Photooxidation of crude oil components is an important process that removes pollutants from the environment. Polycyclic aromatic compounds (PACs) are known to be toxic to many life forms, but little is known about their photooxidation products in the aqueous phase. We here identify a large number of photoproducts from 11 benzothiophenes, a polycyclic aromatic sulfur heterocycle that is a major representative of PACs in crude oil. The investigated compounds contain two to four methyl groups and an ethyl or an n-octyl group. In water, the products arise through oxidation of alkyl side chains to aldehydes and carboxylic acids or through an opening in one of the aromatic rings. The product analysis was performed using gas chromatography with mass spectrometric or atomic emission detection. The main product is always a sulfobenzoic acid, which strongly lowers the pH of the solution. With long alkyl substituents, surfactants are formed, which may possess solubilizing properties in water. The larger the number of alkyl groups, the faster is the photooxidation. Several of the identified acidic compounds were also found when whole crude oil was photooxidized, showing that simulation with individual compounds reflects the situation in whole crude.

Study of weathering effects on the distribution of aromatic steroid hydrocarbons in crude oils and oil residues.

PubMed

Wang, Chuanyuan; Chen, Bing; Zhang, Baiyu; Guo, Ping; Zhao, Mingming

2014-01-01

The composition and distribution of triaromatic steroid hydrocarbons in oil residues after biodegradation and photo-oxidation processes were detected, and the diagnostic ratios for oil spill identification were developed and evaluated based on the relative standard deviation (RSD) and the repeatability limit. The preferential loss of C27 methyl triaromatic steranes (MTAS) relative to C28 MTAS and C29 MTAS was shown during the photo-oxidation process. In contrast to the photochemical degradation, the MTAS with the original 20R biological configuration was preferentially degraded during the biodegradation process. The RSD of most of the diagnostic ratios of MTAS ranged from 9 to 84% during the photo-oxidation process. However, the RSDs of such ratios derived from MTAS were all <5% even in high biodegradation, and such parameters may also provide new methods on oil spill identification. The parameters of monoaromatic sterane and monoaromatic sterane are not used well for oil spill identification after photo-oxidation. The triaromatic steroid hydrocarbons retained their molecular compositions after biodegradation and photo-oxidation and most of the diagnostic ratios derived from them could be efficiently used in oil spill identification.

Photophysical and Photochemical Properties of 3-methylpterin as a New and More Stable Pterin-type Photosensitizer.

PubMed

Estébanez, Sandra; Lorente, Carolina; Kaufman, Teodoro S; Larghi, Enrique L; Thomas, Andrés H; Serrano, Mariana P

2018-05-04

Pterin derivatives are heterocyclic compounds which are present in different biological systems. Neutral aqueous solutions of pterins presents acid-base and keto-enol equilibria. These compounds under UV-A radiation fluoresce, undergo photooxidation, generate reactive oxygen species, and photoinduce the oxidation of biological substrates. As photosensitizers, they may act through different mechanisms; mainly through an electron-transfer initiated process (type I mechanism), but they also produce singlet molecular oxygen ( 1 O 2 ) upon irradiation (type II mechanism). In general, upon UV-A excitation two triplet states, corresponding to the lactim and lactam tautomers, are formed, but only the last one is the responsible for the photosensitized reactions of biomolecules. We present a study of the photochemical properties of 3-methylpterin (3-Mep) which, in contrast to most pterin derivatives, exists only in the lactam form. Also an improvement in the synthesis of 3-Mep is reported. The spectroscopic properties 3-Mep in aqueous solution were similar to those of the unsubstituted pterin derivative (Ptr) in its acid form, such as absorption, fluorescent and phosphorescent emission spectra. Experiments using 2'-deoxyguanosine 5'-monophosphate (dGMP) as oxidizable target, demonstrated that methylation at C-3 position of the pterin moiety does not affect significantly the efficiency of photosensitization, but results in a more photostable sensitizer. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

[Photooxidation of P700 in photosystem 1 preparations with various amounts of antenna chlorophyll a].

PubMed

Il'ina, M D; Borisov, A Iu

1982-12-01

A number of membrane fragments and pigment-protein complexes of photosystem 1 was obtained from pea chloroplasts, using ionic and non-ionic detergents (SDS, digitonin, Triton X-100, lauryldimethylamine-N-oxide). The ratio of chlorophyll (Chl) a to P700 varied from 220 to 30. For non-dialyzed preparations the quantum yield of P700 photooxidation (phi e) measured by the initial rate of photobleaching at 696-698 nm with excitation at the Soret band of Chla was equal to 40-60%. When the P700 photooxidation was measured at 432 nm, the phi e value showed a further decrease to 20-40% during red light excitation over the range of 660-680 nm but rose to 70-90% at the exciting light wavelengths of greater than or equal to 695 nm. On the basis of the observed dependences the red absorption band was approximated by a sum of two spectra: the spectrum of Chla photoactive in P700 photooxidation and that of photoinactive Chla. Both spectra had maxima near the absorption peak of the object. The photoinactive fraction was additionally enriched by the long-wavelength absorption forms of Chla with an absorption maximum over the range of 684-690 nm. The amount of the bulk Chla in the photoinactive fraction was no less than 40%. The phi e value for freshly dialyzed preparation at a Chla/P700 ratio of 30 was equal to 50-60% independent of the exciting light wavelength. An addition of 0.05% Triton X-100 to this preparation caused: i) a blue shift of the absorption and fluorescence maxima; ii) a decrease of the long-wavelength absorption forms content of Chla and, iii) a considerable increase in fluorescence lifetime and quantum yield due to deaggregation of Chla and its solubilization by detergent micelles. The same phenomenon seems to be responsible for the formation of photoinactive fraction of a pigment, since after addition of a detergent the above-mentioned spectral dependence of phi e appeared, i.e. phi e showed a 3-fold decrease (down to 18%) within the region of 660-680 nm and a 1,6-fold increase (up to 90%) at 705-730 nm. These results suggest that the detergents destroy the intact construction of a light-harvesting antenna rather than that of the photosystem 1 reaction center.

Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides

PubMed Central

Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O. T.; Zhang, Zhenfa; Marth, Wendy J.; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G.; Vizuete, William; Xie, Ying; Luecken, Deborah J.; Piletic, Ivan R.; Edney, Edward O.; Bartolotti, Libero J.; Gold, Avram; Surratt, Jason D.

2013-01-01

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx. PMID:23553832

Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides.

PubMed

Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O T; Zhang, Zhenfa; Marth, Wendy J; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G; Vizuete, William; Xie, Ying; Luecken, Deborah J; Piletic, Ivan R; Edney, Edward O; Bartolotti, Libero J; Gold, Avram; Surratt, Jason D

2013-04-23

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO(x) = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO(x).

Kinetics of 25-hydroperoxycholesterol formation during photo-oxidation of crystalline cholesterol.

PubMed

Medina-Meza, Ilce Gabriela; Rodriguez-Estrada, Maria Teresa; Lercker, Giovanni; Barnaba, Carlo; García, Hugo Sergio

2014-06-01

25-Hydroxycholesterol (25-OH), a side-chain product of cholesterol oxidation, has emerged as one of the important issues in food chemistry and biochemistry, because of its involvement in several human pathologies. This oxysterol is derived from both enzymatic and non-enzymatic pathways. However, the latter mechanism has been scarcely studied in either food or model systems. In this work, a kinetic model was developed to evaluate the formation of 25-OH and its precursor 25-hydroperoxycholesterol (25-OOH) during photo-oxidation of cholesterol for 28 days under fluorescent light. 25-OOH was estimated by an indirect method, using thin-layer chromatography coupled with gas chromatography-mass spectrometry. Peroxide value (POV) and cholesterol oxidation products (COPs) were determined. POV showed a hyperbolic behavior, typical of a crystalline system in which the availability of cholesterol is the limiting factor. Further reactions of hydroperoxides were followed; in particular, after photo-oxidation, 25-OOH (0.55 mg g(-1) ) and 25-OH (0.08 mg g(-1) ) were found in cholesterol, as well as seven other oxysterols, including 7-hydroxy and 5,6-epoxy derivatives. The application of kinetic models to the data showed good correlation with theoretical values, allowing derivation of the kinetic parameters for each oxidation route. The results of this work confirm that cholesterol in the crystalline state involves different oxidation patterns as compared to cholesterol in solution. Moreover, the numerical fit proved that hydroperoxidation is the rate-limiting step in 25-OH formation. © 2013 Society of Chemical Industry.

Catalytic Properties of Fe-containing Layered Aluminosilicates in Photo-oxidation of Dye “Methyl Green”

NASA Astrophysics Data System (ADS)

Shadrina, O. A.; Dashinamzhilova, E. Ts; Khankhasaeva, S. Ts

2017-11-01

The iron-containing materials with an iron content of 40 mg/g and 52.5 mg/g, a specific surface area of 107 m2/g and 96 m2/g are developed on the basis of natural layered aluminosilicate (montmorillonite) and polyhydroxo complexes of iron. It is shown that the materials exhibit high catalytic activity in the photo-oxidation of dye “Methyl Green”. The influence of physicochemical parameters (loading of the catalyst, a ratio of initial concentrations [H2O2]/[MG] on the efficiency of the dye photo-oxidation was established. The optimum conditions, which made it possible to achieve high mineralization and 100 % the dye oxidation efficiency were determined: the catalyst loading equal to 1.0 g/l and the ratio of [H2O2] and [MG] equal to stoichiometric ratio (55 mol/mol). The decrease of the total organic carbon content after photo-oxidation reaction was 56.5%. The average value of the quantum yield of the dye photo-oxidation was to 0.30 mol/Einstein. The results of the conducted research show that the developed iron-containing materials are the promising catalysts for photo-Fenton processes of oxidative degradation of organic compounds. The materials are of interest for use in wastewater treatment processes from toxic organic pollutants.

An experimental study on ferrous iron photo-oxidation: Effect of the solar spectrum on the surface for acidification of surface water in the early Hesperian Mars

NASA Astrophysics Data System (ADS)

Tabata, H.; Sekine, Y.; Kanzaki, Y.; Sugita, S.; Murakami, T.

2017-12-01

Geochemical evidence obatined by Mars Opportunity rover suggests that the pH of Martian surface water shifted to highly acidic, i.e., pH 2-4, in the early Hesperian (e.g., Tosca et al., 2005). Hurowitz et al. (2010) proposed that solar UV light may have promoted the acidification through photo-oxidation of ferrous iron dissolved in upwelling groundwater on early Mars. However, the trigger for the acidification in the early Hesperian remains unclear. The photo-oxidation of Fe2+ occurs under acidic conditions, i.e., pH < 3 (Jortner et al., 1962); however, the pH of upwelling groundwater would be neutral to alkaline (Zolotov et al., 2016). At neutral to alkaline pH, FeOH+ can exist together with Fe2+ in a solution. While both Fe2+ and FeOH+ are photo-oxidized only by UV light (< 300 nm), FeOH+ can also be photo-oxidized by long UV/visible light (300-400 nm). Thus, the efficiency of acidification through photo-oxidation on early Mars should have depended on the solar spectrum on the surface at that time which is determined by the atmospheric composition. To investigate the effect of UV spectrum on the acidification, we conducted two types of laboratory experiments: One used a Xe lamp as the light source for photo-oxidation of ferrous iron to irradiate light with continuous spectrum from 250 to 400 nm, and the other used the Xe lamp with an optical filter that cuts off UV light shorter than 300 nm. The pH value of the starting solution was around 7. Upon the UV irradiation covering full wavelength range (250-400 nm), the pH value of the solution decreases down to less than 4, consistent with the proposed pH of the Hesperian acidic water on Meridiani Planum (Tosca et al., 2005). This occurs because Fe2+ is stable at pH < 5, and because Fe2+ can be continuously photo-oxidized in the acidic solution by UV light in 250-300 nm. When the UV irradiation covering 300-400 nm, the pH value of the solution also decreases to pH 5 immediately after the UV irradiation. However, it does not decrease less than pH 5 and reaches a steady state. This is the case because FeOH+ is converted into Fe2+ at low pH, which prevents further photo-oxidation by light in 300-400 nm. These results suggest that a change in the atmospheric composition and consequent reaching of UV light in the wavelength < 300 nm may have played a key role for triggering the acidification in the early Hesperian.

Protective Action of Spermine and Spermidine against Photoinhibition of Photosystem I in Isolated Thylakoid Membranes

PubMed Central

Yaakoubi, Hnia; Hamdani, Saber; Bekalé, Laurent; Carpentier, Robert

2014-01-01

The photo-stability of photosystem I (PSI) is of high importance for the photosynthetic processes. For this reason, we studied the protective action of two biogenic polyamines (PAs) spermine (Spm) and spermidine (Spd) on PSI activity in isolated thylakoid membranes subjected to photoinhibition. Our results show that pre-loading thylakoid membranes with Spm and Spd reduced considerably the inhibition of O2 uptake rates, P700 photooxidation and the accumulation of superoxide anions (O2 −) induced by light stress. Spm seems to be more effective than Spd in preserving PSI photo-stability. The correlation of the extent of PSI protection, photosystem II (PSII) inhibition and O2 − generation with increasing Spm doses revealed that PSI photo-protection is assumed by two mechanisms depending on the PAs concentration. Given their antioxidant character, PAs scavenge directly the O2 − generated in thylakoid membranes at physiological concentration (1 mM). However, for non-physiological concentration, the ability of PAs to protect PSI is due to their inhibitory effect on PSII electron transfer. PMID:25420109

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy

NASA Astrophysics Data System (ADS)

Hall, James P.; Poynton, Fergus E.; Keane, Páraic M.; Gurung, Sarah P.; Brazier, John A.; Cardin, David J.; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V.; Towrie, Michael; Cardin, Christine J.; Kelly, John M.; Quinn, Susan J.

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides

PubMed Central

Kim, J. Dongun; Yee, Nathan; Nanda, Vikas; Falkowski, Paul G.

2013-01-01

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth’s history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth. PMID:23733945

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy.

PubMed

Hall, James P; Poynton, Fergus E; Keane, Páraic M; Gurung, Sarah P; Brazier, John A; Cardin, David J; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V; Towrie, Michael; Cardin, Christine J; Kelly, John M; Quinn, Susan J

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Empirical Analysis of the Photoelectrochemical Impedance Response of Hematite Photoanodes for Water Photo-oxidation.

PubMed

Klotz, Dino; Grave, Daniel A; Dotan, Hen; Rothschild, Avner

2018-03-15

Photoelectrochemical impedance spectroscopy (PEIS) is a useful tool for the characterization of photoelectrodes for solar water splitting. However, the analysis of PEIS spectra often involves a priori assumptions that might bias the results. This work puts forward an empirical method that analyzes the distribution of relaxation times (DRT), obtained directly from the measured PEIS spectra of a model hematite photoanode. By following how the DRT evolves as a function of control parameters such as the applied potential and composition of the electrolyte solution, we obtain unbiased insights into the underlying mechanisms that shape the photocurrent. In a subsequent step, we fit the data to a process-oriented equivalent circuit model (ECM) whose makeup is derived from the DRT analysis in the first step. This yields consistent quantitative trends of the dominant polarization processes observed. Our observations reveal a common step for the photo-oxidation reactions of water and H 2 O 2 in alkaline solution.

A New Low Cost Wide-Field Illumination Method for Photooxidation of Intracellular Fluorescent Markers

PubMed Central

da Silva Filho, Manoel; Santos, Daniel Valle Vasconcelos; Costa, Kauê Machado

2013-01-01

Analyzing cell morphology is crucial in the fields of cell biology and neuroscience. One of the main methods for evaluating cell morphology is by using intracellular fluorescent markers, including various commercially available dyes and genetically encoded fluorescent proteins. These markers can be used as free radical sources in photooxidation reactions, which in the presence of diaminobenzidine (DAB) forms an opaque and electron-dense precipitate that remains localized within the cellular and organelle membranes. This method confers many methodological advantages for the investigator, including absence of photo-bleaching, high visual contrast and the possibility of correlating optical imaging with electron microscopy. However, current photooxidation techniques require the continuous use of fluorescent or confocal microscopes, which wastes valuable mercury lamp lifetime and limits the conversion process to a few cells at a time. We developed a low cost optical apparatus for performing photooxidation reactions and propose a new procedure that solves these methodological restrictions. Our “photooxidizer” consists of a high power light emitting diode (LED) associated with a custom aluminum and acrylic case and a microchip-controlled current source. We demonstrate the efficacy of our method by converting intracellular DiI in samples of developing rat neocortex and post-mortem human retina. DiI crystals were inserted in the tissue and allowed to diffuse for 20 days. The samples were then processed with the new photooxidation technique and analyzed under optical microscopy. The results show that our protocols can unveil the fine morphology of neurons in detail. Cellular structures such as axons, dendrites and spine-like appendages were well defined. In addition to its low cost, simplicity and reliability, our method precludes the use of microscope lamps for photooxidation and allows the processing of many labeled cells simultaneously in relatively large tissue samples with high efficacy. PMID:23441199

Highly sensitive microfluidic paper-based photoelectrochemical sensing platform based on reversible photo-oxidation products and morphology-preferable multi-plate ZnO nanoflowers.

PubMed

Kong, Qingkun; Wang, Yanhu; Zhang, Lina; Xu, Caixia; Yu, Jinghua

2018-07-01

A microfluidic paper-based analytical device (μPAD) was simply constructed for highly sensitive detection of L-glutamic acid and L-cysteine. The μPAD featured with two functional zones on one strip of paper achieved by preferable multi-plate ZnO nanoflowers (ZnO NFs) and molecularly imprinting polymer (MIP) membranes. The as-designed μPAD was established based on the inherent relation between the photo-oxidation products and photoelectrochemical (PEC) performance with the highly sensitive detection of biomolecules. The ZnO NFs were utilized to produce photo-oxidation products by driving the reaction between ferrocenemethanol and photogenerated holes under ultraviolet light. The photo-oxidation products easily flowed to MIP membranes along the hydrophilic channel via capillary action. MIP membranes as the receptors specifically recognized the analytes as well as decreased the electron loss by blocking the reduction reaction between electrons and photo-oxidation products. The PEC response was obtained in the processes of electrons transfer and exhibited the direct relationships corresponding to the concentrations of target analytes. The μPAD showed the detection limits toward L-glutamic acid and L-cysteine as low as 9.6 pM and 24 pM, respectively. Moreover, it is interesting to point out that ZnO NFs nanostructure shows superior PEC signal compared with those of ZnO nanospheres, nanosheets, and nanorod arrays. In current work, photo-oxidation products are utilized to achieve highly sensitive PEC detection for biomolecules under ultraviolet light as well as avoid the effects of multiple modifications in the same region on the reproducibility, which is beneficial for opening up rich possibility for designing more efficient analytical strategy. Copyright © 2018 Elsevier B.V. All rights reserved.

Evaluation of isoprene degradation in the detailed tropospheric chemical mechanism, MCM v3, using environmental chamber data

NASA Astrophysics Data System (ADS)

Pinho, P. G.; Pio, C. A.; Jenkin, M. E.

The isoprene degradation mechanism included in version 3 of the Master Chemical Mechanism (MCM v3) has been evaluated and refined, using the Statewide Air Pollution Research Center (SAPRC) environmental chamber datasets on the photo-oxidation of isoprene and its degradation products, methacrolein (MACR) and methylvinyl ketone (MVK). Prior to this, the MCM v3 butane degradation chemistry was also evaluated using chamber data on the photo-oxidation of butane, and its degradation products, methylethyl ketone (MEK), acetaldehyde (CH 3CHO) and formaldehyde (HCHO), in conjunction with an initial evaluation of the chamber-dependent auxiliary mechanisms for the series of relevant chambers. The MCM v3 mechanisms for both isoprene and butane generally performed well and were found to provide an acceptable reaction framework for describing the NO x-photo-oxidation experiments on the above systems, although a number of parameter modifications and refinements were identified which resulted in an improved performance. All these relate to the magnitude of sources of free radicals from organic chemical process, such as carbonyl photolysis rates and the yields of radicals from the reactions of O 3 with unsaturated oxygenates, and specific recommendations are made for refinements. In addition to this, it was necessary to include a representation of the reactions of O( 3P) with isoprene, MACR and MVK (which were not previously treated in MCM v3), and conclusions are drawn concerning the required extent of free radical formation from these reactions. Throughout the study, the performance of MCM v3 was also compared with that of the SAPRC-99 mechanism, which was developed and optimized in conjunction with the chamber datasets.

Mutagenic atmospheres resulting from the photooxidation of aromatic hydrocarbon and NOx mixtures

EPA Science Inventory

Although many volatile organic compounds (VOCs) are regulated to limit air pollution and the consequent health effects, the photooxidation products generally are not. Thus, we examined the mutagenicity in Salmonella TA100 of photochemical atmospheres generated in a steady-state a...

Optimization of Photooxidative Removal of Phenazopyridine from Water

NASA Astrophysics Data System (ADS)

Saeid, Soudabeh; Behnajady, Mohammad A.; Tolvanen, Pasi; Salmi, Tapio

2018-05-01

The photooxidative removal of analgesic pharmaceutical compound phenazopyridine (PhP) from aqueous solutions by UV/H2O2 system with a re-circulated photoreactor was investigated. Response surface methodology (RSM) was employed to optimize the effect of operational parameters on the photooxidative removal efficiency. The investigated variables were: the initial PhP and H2O2 concentrations, irradiation time, volume of solution and pH. The analysis of variance (ANOVA) of quadratic model demonstrated that the described model was highly significant. The predicted values of the photooxidative removal efficiency were found to be in a fair agreement with experimental values ( R 2 = 0.9832, adjusted R 2 = 0.9716). The model predicted that the optimal reaction conditions for a maximum removal of PhP (>98%) were: initial PhP concentration less than 23 mg L-1, initial concentration of H2O2 higher than 470 mg L-1, solution volume less than 500 mL, pH close to 2 and irradiation time longer than 6 min.

Elongational viscosity of photo-oxidated LDPE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rolón-Garrido, Víctor H., E-mail: victor.h.rolongarrido@tu-berlin.de, E-mail: manfred.wagner@tu-berlin.de; Wagner, Manfred H., E-mail: victor.h.rolongarrido@tu-berlin.de, E-mail: manfred.wagner@tu-berlin.de

2014-05-15

Sheets of low-density polyethylene (LDPE) were photo-oxidatively treated at room temperature, and subsequently characterized rheologically in the melt state by shear and uniaxial extensional experiments. For photo-oxidation, a xenon lamp was used to irradiate the samples for times between 1 day and 6 weeks. Linear-viscoelastic characterization was performed in a temperature range of 130 to 220°C to obtain the master curve at 170°C, the reference temperature at which the elongational viscosities were measured. Linear viscoelasticity is increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by an increasing gel fraction as determined by a solvent extraction method.more » The elongational measurements reveal a strong enhancement of strain hardening until a saturation level is achieved. The elongational data are analyzed in the frame work of two constitutive equations, the rubber-like liquid and the molecular stress function models. Within the experimental window, timedeformation separability is confirmed for all samples, independent of the degree of photo-oxidation.« less

Photo-catalytic oxidation of acetone on a TiO2 powder: An in situ FTIR investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szanyi, János; Kwak, Ja Hun

2015-09-01

In situ transmission infrared spectroscopy was used to investigate the photo-oxidation of acetone on a commercial, oxidized TiO2 (P25) powder catalyst under UV irradiation at ambient temperature, in the absence and presence of gas phase O2. The photochemistry of a number of organic molecules (1-butanone, methanol and acetic acid,) under the same conditions was also studied in order to identify reaction intermediates and products formed in the photo-oxidation of acetone. Under anaerobic conditions (in the absence of gas phase oxygen) limited extent of photo-oxidation of acetone took place on the oxidized TiO2 sample. In the presence of O2 in themore » gas phase, however, acetone was completely converted to acetates and formates, and ultimately CO2. The initial step in the sequence of photo-induced reactions is the ejection of a methyl radical, resulting in the formation of surface acetates (from the acetyl group) and formates (from the methyl radicals). Acetate ions are also converted to formates, that, in turn, photo-oxidized to CO2. Under the experimental conditions applied the accumulation of carbonates and bicarbonates were observed on the TiO2 surface as the photo-oxidation of acetone proceeded (this was also observed during the course of photo-oxidation of all the other organics studied here). When the initial radical ejection step produced hydrocarbons containing more than one C atoms (as in the case in 2-butanone and mesytil oxide), the formation of aldehydes on the catalyst surface was also observed as a result of secondary reactions. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2014 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea). The authors thank M.A. Henderson for the fruitful discussions on the photo-oxidation of organic molecules on TiO2.« less

The Fate of Crude Oil during Photooxidation under Natural Sunlight

NASA Astrophysics Data System (ADS)

Wang, Q.; Evans, M.; Bacosa, H. P.; Hu, X.; Liu, Z.

2016-02-01

Photooxidation plays an important role in removing spilled crude oil, particularly the aromatic fraction, in surface seawater. Even though much research has been done regarding the changes of different oil fractions by photooxidation, including saturate, aromatic, resin and asphaltene (SARA), we know little about how specific aromatic compounds change in the SARA fractions during photooxidation. In this study, we amended 13C-labled phenanthrene in slightly weathered Louisiana light sweet crude, and followed the fates of 13C values of the SARA fractions during a 44-d incubation experiment under the natural sunlight in south Texas. Our results showed that the aromatic fraction of the crude decreased from 25.4% at time zero to 13.5% at the 44th d, while the resin increased from 12.2% to 16.5% and asphaltene from 2.4% to 13.3%, respectively. This result indicates the aromatic was transformed mostly into asphaltene by photooxidation, and most of the changes took place within the first 10 d. In contrast, no significant difference was observed in the SARA fractions in the dark controls. Analyses of 13C values and phenanthrene concentrations in the SARA fractions are currently on going and will be presented. Results from this experiment provide insights into changes of specific aromatic compounds within oil fractions by photochemical oxidation during oil weathering in the ocean.

TREATMENT OF METHYL TERT-BUTYL ETHER CONTAMINATED WATER USING PHOTOCATALYSIS

EPA Science Inventory

The feasibility of photo-oxidation treatment of methyl tert-butyl ether (MTBE) in water was investigated in three ways, 1) using a slurry falling film photo-reactor, 2) a batch solar reactor system, and 3) a combination of air-stripping and gas phase photooxidation system. MTBE-c...

DETERMINATION OF SECONDARY ORGANIC AEROSOL PRODUCTS FROM THE PHOTOOXIDATION OF TOLUENE AND THEIR IMPLICATIONS IN AMBIENT PM2.5

EPA Science Inventory

Laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NOX/air mixtures in a smog chamber operated in the dynamic mode...

Molecular Responses to Photooxidative Stress in Pinus sylvestris (L.) (II. Differential Expression of CuZn-Superoxide Dismutases and Glutathione Reductase.

PubMed Central

Karpinski, S.; Wingsle, G.; Karpinska, B.; Hallgren, J. E.

1993-01-01

The influence of photooxidative stress on genes expressing superoxide dismutase (Sod) and glutathione reductase (Gor) was analyzed in needles of top and side shoots of 3-year-old Pinus sylvestris (L.) seedlings. The study was carried out in the field during spring recovery. From mid-April the top shoots of seedlings protruded above the snow and thus were exposed to sunlight, whereas the side shoots were covered with snow until May 4. Needles were sampled from top and side shoots on five different occasions. At the beginning of May the mRNA levels for cytosolic CuZn-Sod were significantly higher in top-shoot needles than in side-shoot needles. Similar results were obtained for chloroplastic CuZn-Sod mRNA. After May 6 we could not detect any significant differences between top- and side-shoot needles for either CuZn-Sod mRNA level. Transcript accumulation for the chloroplastic CuZn-Sod was up to 4-fold higher than for cytosolic CuZn-Sod in both types of shoots. On June 1 minimum transcript levels were observed for both CuZn-SOD isoforms. Protein activity analysis for CuZn-SOD isozymes did not reveal any significant differences between top- and side-shoot needles during the whole period of measurements. The mRNA level for chloroplastic Gor was similar in both types of shoots. However, the total GR activity was significantly higher in top-shoot needles than in side-shoot needles at the beginning of May. The analysis of mRNA accumulation for chloroplastic CuZn-Sod and Gor indicates that transcript levels were at least 5- to 20-fold higher for CuZn-Sod than for chloroplastic Gor. The differential expressions of Sod and Gor genes are discussed in relation to regulation of the enzymic scavenging system during photooxidative stress conditions. PMID:12232032

Responses to clomazone and 5-ketoclomazone by Echinochloa phyllopogon resistant to multiple herbicides in Californian rice fields.

PubMed

Yasuor, Hagai; TenBrook, Patti L; Tjeerdema, Ronald S; Fischer, Albert J

2008-10-01

Late watergrass [Echinochloa phyllopogon (Stapf.) Koss.] is a major weed of Californian rice that has evolved P450-mediated metabolic resistance to multiple herbicides. Resistant (R) populations are also poorly controlled by the recently introduced herbicide clomazone. The authors assessed whether this cross-resistance was also P450 mediated, and whether R plants also had reduced sensitivity to photooxidation. Understanding mechanism(s) of resistance facilitates the design of herbicide management strategies to delay resistance evolution. Ratios (R/S) of R to susceptible (S) GR(50) were near 2.0. [(14)C]Clomazone uptake was similar in R and S plants. Clomazone and its metabolite 5-ketoclomazone reduced chlorophyll and carotenoids in S more than in R plants. The P450 inhibitors disulfoton and 1-aminobenzo-triazole (ABT) safened clomazone in R and S plants. Disulfoton safened 5-ketoclomazone only in S plants, while ABT synergized 5-ketoclomazone mostly against S plants. Paraquat was more toxic in S than in R plants. Cross-resistance to clomazone explains failures to control R plants in rice fields, and safening by P450 inhibitors suggests that oxidative activation of clomazone is needed for toxicity to E. phyllopogon. Clomazone resistance requires mitigation of 5-ketoclomazone toxicity, but P450 detoxification may not significantly confer resistance, as P450 inhibitors poorly synergized 5-ketoclopmazone in R plants. Responses to paraquat suggest research on mechanisms to mitigate photooxidation in R and S plants is needed.

Shear and elongational rheology of photo-oxidative degraded HDPE and LLDPE

NASA Astrophysics Data System (ADS)

Wagner, Manfred Hermann; Zheng, Wang; Wang, Peng; Talamante, Sebastián Ramos; Narimissa, Esmaeil

2017-05-01

The effect of photo-oxidative degradation of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) was investigated by linear and non-linear rheological measurements. The linear-viscoelastic rheological measurements were performed at different temperatures, while the elongational viscosity was measured at 170°C and at different strain rates. The rheological data are indicative of structural changes caused by photo-oxidative degradation including formation of long-chain branches (LCB), cross-linking, and chain scission, and they revealed a cyclic and continuing competition between chain scission and LCB/gel formation. These findings are supported by additional FTIR measurements and direct measurements of the gel content of the degraded samples.

Solar photo-oxidative disinfection of drinking water: preliminary field observations.

PubMed

Reed, R H; Mani, S K; Meyer, V

2000-06-01

The feasibility of using solar photo-oxidation to inactivate faecal bacterial contaminants in drinking water has been evaluated under field conditions in India and South Africa. Freshly drawn samples from all six test water sources were low in dissolved oxygen, at 13-40% of the air saturation value. However, vigorous mixing followed by exposure to full-strength sunlight in transparent plastic containers (1-25 l capacity) caused a rapid decrease in the counts of faecal indicator bacteria, giving complete inactivation within 3-6 h, with no evidence of reactivation. These results demonstrate that solar photo-oxidation may provide a practical, low-cost approach to the improvement of drinking water quality in developing countries with consistently sunny climates.

VOC removal and deodorization of effluent gases from an industrial plant by photo-oxidation, chemical oxidation, and ozonization.

PubMed

Domeño, Celia; Rodríguez-Lafuente, Angel; Martos, J M; Bilbao, Rafael; Nerín, Cristina

2010-04-01

The efficiency of photo-oxidation, chemical oxidation by sodium hypochlorite, and ozonization for the industrial-scale removal of volatile organic compounds (VOCs) and odors from gaseous emissions was studied by applying these treatments (in an experimental system) to substances passing through an emission stack of a factory producing maize derivatives. Absorption and ozonization were the most efficient treatment, removing 75% and 98% of VOCs, respectively, while photo-oxidation only removed about 59%. The emitted chemical compounds and odors were identified and quantified by gas chromatography-mass spectrometry (in full-scan mode). In addition to presenting the results, their implications for selecting optimal processes for treating volatile emissions are discussed.

PHOTOOXIDATION AND ITS EFFECTS ON THE CARBOXYL CONTENT OF DISSOLVED ORGANIC MATTER IN TWO COASTAL RIVERS IN THE SOUTHEASTERN UNITED STATES

EPA Science Inventory

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 (ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study the quantitative relationships were investigated ...

HYDROGEN PEROXIDE FORMATION FROM THE PHOTOOXIDATION OF FORMALDEHYDE AND ITS PRESENCE IN RAINWATER

EPA Science Inventory

The photooxidation of formaldehyde with sunlamps (E(max) = 3100 A) produces hydrogen peroxide (H2O2) at varying concentrations depending upon the amount of water vapor present. It is postulated that the variable production of H2O2 is a result of condensation on the reactor surfac...

MOLECULAR SPECIATION OF SECONDARY ORGANIC AEROSOL FROM PHOTOOXIDATION OF THE HIGHER ALKENES: 1-OCTENE AND 1-DECENE. (R824970)

EPA Science Inventory

Outdoor smog chamber photooxidations to determine the molecular composition of secondary organic aerosol (SOA) from 1-octene and 1-decene in sunlight-irradiated hydrocarbon-NO_x mixtures are reported. The observed products are consistent with the current under...

Selective photooxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, Heinz; Blatter, Fritz; Sun, Hai

1998-01-01

A selective photooxidation process for the conversion of hydrocarbon molecules to partially oxygenated derivatives, which comprises the steps of adsorbing a hydrocarbon and oxygen onto a dehydrated zeolite support matrix to form a hydrocarbon-oxygen contact pair, and subsequently exposing the hydrocarbon-oxygen contact pair to visible light, thereby forming a partially oxygenated derivative.

Functionalization of Single-Wall Carbon Nanotubes by Photo-Oxidation

NASA Technical Reports Server (NTRS)

Lebron-Colon, Marisabel; Meador, Michael A.

2010-01-01

new technique for carbon nanotube oxidation was developed based upon the photo-oxidation of organic compounds. The resulting method is more benign than conventional oxidation approaches and produces single-wall carbon nanotubes (SWCNTs) with higher levels of oxidation. In this procedure, an oxygen saturated suspension of SWNTs in a suitable solvent containing a singlet oxygen sensitizer, such as Rose Bengal, is irradiated with ultraviolet light. The resulting oxidized tubes are recovered by filtering the suspension, followed by washing to remove any adsorbed solvent and sensitizer, and drying in a vacuum oven. Chemical analysis by FT-infrared and x-ray photoelectron spectroscopy revealed that the oxygen content of the photo-oxidized SWCNT was 11.3 atomic % compared to 6.7 atomic % for SWCNT that had been oxidized by standard treatment in refluxing acid. The photo-oxidized SWCNT produced by this method can be used directly in various polymer matrixes, or can be further modified by chemical reactions at the oxygen functional groups and then used as additives. This method may also be suitable for use in oxidation of multiwall carbon nanotubes and graphenes.

Perturbations in carotenoid and porphyrin status result in differential photooxidative stress signaling and antioxidant responses.

PubMed

Park, Joon-Heum; Jung, Sunyo

2018-02-12

We examined differential photooxidative stress signaling and antioxidant responses in rice plants treated with norflurazon (NF) and oxyfluorfen (OF), which are inhibitors of carotenoid and porphyrin biosynthesis, respectively. Plants treated with OF markedly increased levels of cellular leakage and malondialdehyde, compared with NF-treated plants, showing that OF plants suffered greater oxidative damage with respect to membrane integrity. The enhanced production of H 2 O 2 in response to OF, but not NF, indicates the important role of H 2 O 2 in activation of photooxidative stress signaling in OF plants. In response to NF and OF, the increased levels of free salicylic acid as well as maintenance of the redox ratio of ascorbate and glutathione pools to a certain level are considered to be crucial factors in the protection against photooxidation. Plants treated with OF greatly up-regulated catalase (CAT) activity and Cat transcript levels, compared with NF-treated plants. Interestingly, NF plants showed no noticeable increase in oxidative metabolism, although they did show considerable increases in ascorbate peroxidase (APX) and peroxidase activities and transcript levels of APX, as in OF plants. Our results suggest that perturbations in carotenoid and porphyrin status by NF and OF can be sensed by differential photooxidative stress signaling, such as that involving H 2 O 2 , redox state of ascorbate and glutathione, and salicylic acid, which may be responsible for at least part of the induction of ROS-scavenging enzymes. Copyright © 2018 Elsevier Inc. All rights reserved.

Degradation of polycyclic aromatic hydrocarbons (PAHs) present in used motor oil and implications for urban runoff quality

NASA Astrophysics Data System (ADS)

Ferreira, M.; Stenstrom, M. K.; Lau, S.

2013-12-01

Polycyclic aromatic hydrocarbons (PAHs) are common organic pollutants of urban stormwater runoff due to atmospheric deposition, vehicle-related discharges, and coal tar pavement sealants. The US EPA lists sixteen PAHs as priority pollutants and seven of those are potential carcinogenic compounds. Due to their molecular structure, PAHs tend to attach to particles that will subsequently be deposited as sediments in waterways. This study focuses on the degradation of PAHs present in used motor oil. Four experimental setups were used to simulate volatilization and photooxidation in the degradation of sixteen PAHs as observed for up to 54 days. The volatilization-only experiment showed substantial reduction only in the concentration of Napthalene (Nap). However, photooxidation-only was more efficient in degrading PAHs. In this process, substantial reduction in the concentrations of Nap, Acenapthene (Anthe), Anthracene (ANT), Fluoranthene (FLT), Pyrene (PYR), Benz[a]anthracene (BaA), Benzo[a]pyrene (BaP), Indeno[1,2,3,cd]pyrene (INP), and Benz[g,h,i]perylene (BghiP) were observed as early as five days. The two volatilization-photooxidation experiments exhibited substantial reduction in the concentrations of Fluorene (FLU), Chrysene (CHR) and Benzo[b]fluoranthene (BbF), in addition to the PAHs reduced by photooxidation-only. Phenanthrene (PHE), Fluoranthene (FLT), and Benzo[b]fluoranthene (BbF) only exhibited substantial decreased concentrations after 20 days in the volatilization-photooxidation experiment. One PAH, acenapthylene (Anthy), was not detected in the original sample of used motor oil. The highest degradations were observed in the combined volatilization-photooxidation experiment. In regions with infrequent rainfall, such as Southern California, molecules of PAHs attached to highway particles will have time to undergo degradation prior to transport. Therefore, PAHs may be present in lower concentrations in highway runoff in dry climates than in rainy climates. To support this hypothesis, a review of highway-related PAHs concentrations is presented.

Elongational rheology and cohesive fracture of photo-oxidated LDPE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rolón-Garrido, Víctor H., E-mail: victor.h.rolongarrido@tu-berlin.de; Wagner, Manfred H.

2014-01-15

It was found recently that low-density polyethylene (LDPE) samples with different degrees of photo-oxidation represent an interesting system to study the transition from ductile to cohesive fracture and the aspects of the cohesive rupture in elongational flow. Sheets of LDPE were subjected to photo-oxidation in the presence of air using a xenon lamp to irradiate the samples for times between 1 day and 6 weeks. Characterisation methods included Fourier transform infrared spectroscopy, solvent extraction method, and rheology in shear and uniaxial extensional flows. Linear viscoelasticity was increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by themore » carbonyl index, acid and aldehydes groups, and gel fraction. The molecular stress function model was used to quantify the experimental data, and the nonlinear model parameter β was found to be correlated with the gel content. The uniaxial data showed that the transition from ductile to cohesive fracture was shifted to lower elongational rates, the higher the gel content was. From 2 weeks photo-oxidation onwards, cohesive rupture occurred at every strain rate investigated. The true strain and true stress at cohesive fracture as well as the energy density applied to the sample up to fracture were analyzed. At low gel content, rupture was mainly determined by the melt fraction while at high gel content, rupture occurred predominantly in the gel structure. The strain at break was found to be independent of strain rate, contrary to the stress at break and the energy density. Thus, the true strain and not the stress at break or the energy density was found to be the relevant physical quantity to describe cohesive fracture behavior of photo-oxidated LDPE. The equilibrium modulus of the gel structures was correlated with the true strain at rupture. The stiffer the gel structure, the lower was the deformation tolerated before the sample breaks.« less

Comparison of Experimenal Photooxidation Rates and Patterns in Glass- and Water-Based Oil Slicks with Daily Weathering Observed in the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Sharpless, C.; Aeppli, C.; Reddy, C. M.; Swarthout, B.; Stewart, O. C.; Walters, M.; Valentine, D. L.

2016-02-01

Photooxidation is a well-known degradation route for toxic components of oil (e.g., PAHs). However, recent research suggests that it may play a broader role by enhancing oil's dark1 and photo-toxicity2 and producing persistent, oxidized hydrocarbons.3To better understand photooxidation's importance to oil weathering in marine systems, we are combining laboratory studies with field measurements of compositional changes under controlled conditions. Lab experiments have employed a solar simulator to photooxidize slicks of Dorado Well crude oil on water (Instant Ocean) and glass surfaces. Qualitatively similar compositional changes were seen in both systems, such as rapid loss of aromatics and production of oxidized hydrocarbons as assessed by GCMS, GCxGC, TLC-FID, and FTIR. Rates were much faster on water, a finding tentatively ascribed to the film on glass ( 750 um) being much thicker than on water ( 140 um). Further experiments have been conducted with thinner films on glass, and the results are being analyzed to clarify the importance of film thickness versus surface substrate for photoxidation kinetics. Naturally weathered samples were also collected in the Gulf during a cruise in June, 2015. Surface slicks from natural seeps were tracked and sampled daily under very calm seas with full sun, and solar irradiance was simultaneously measured. These samples, currently undergoing GCxGC and TLC-FID analyses, provide a unique reference with which to assess in-situ transformation rates and compositional changes due to photooxidation. Comparison between results from the field samples and lab experiments should help clarify the absolute contribution of photooxidation to marine oil weathering and improve efforts to use lab results to constrain estimates of environmental transformation rates. 1. D. Rial et al. J. Haz. Mat. 2013, 260, 67 2. J.P. Incardona et al. Proc. Natl. Acad. Sci. 2012, 109, E51 3. C. Aeppli et al. Environ. Sci. Technol. 2012, 46, 8799

Effective absorption cross sections and photolysis rates of anthropogenic and biogenic secondary organic aerosols

NASA Astrophysics Data System (ADS)

Romonosky, Dian E.; Ali, Nujhat N.; Saiduddin, Mariyah N.; Wu, Michael; Lee, Hyun Ji (Julie); Aiona, Paige K.; Nizkorodov, Sergey A.

2016-04-01

Mass absorption coefficient (MAC) values were measured for secondary organic aerosol (SOA) samples produced by flow tube ozonolysis and smog chamber photooxidation of a wide range of volatile organic compounds (VOC), specifically: α-pinene, β-pinene, β-myrcene, d-limonene, farnesene, guaiacol, imidazole, isoprene, linalool, ocimene, p-xylene, 1-methylpyrrole, and 2-methylpyrrole. Both low-NOx and high-NOx conditions were employed during the chamber photooxidation experiments. MAC values were converted into effective molecular absorption cross sections assuming an average molecular weight of 300 g/mol for SOA compounds. The upper limits for the effective photolysis rates of SOA compounds were calculated by assuming unity photolysis quantum yields and convoluting the absorption cross sections with a time-dependent solar spectral flux. A more realistic estimate for the photolysis rates relying on the quantum yield of acetone was also obtained. The results show that condensed-phase photolysis of SOA compounds can potentially occur with effective lifetimes ranging from minutes to days, suggesting that photolysis is an efficient and largely overlooked mechanism of SOA aging.

Effect of Furan Fatty Acids and 3-Methyl-2,4-nonanedione on Light-Induced Off-Odor in Soybean Oil.

PubMed

Sano, Takashi; Okabe, Ryo; Iwahashi, Maiko; Imagi, Jun; Sato, Toshiro; Yamashita, Toshiyuki; Fukusaki, Eiichiro; Bamba, Takeshi

2017-03-15

Soybean oil is one of the most widely consumed vegetable oils. However, under photooxidative conditions, this oil develops a beany and green off-odor through a mechanism that has not yet been elucidated. Upon photooxidation, 3-methyl-2,4-nonanedione (3-MND) produces a strong aroma. In this study, the effect of furan fatty acids and 3-MND on odor reversion in soybean oil was investigated. Our findings suggest that the observed light-induced off-odor was likely attributable to the furan fatty acids present in the oil through the generation of 3-MND. While 3-MND may not be directly responsible for the development of light-induced off-odor, this compound appears to be involved because off-odor was detected in canola oil samples containing added 3-MND. In addition, in the present work, 3-hydroxy-3-methyl-2,4-nonanedione, which is derived from 3-MND, was identified for the first time in light-exposed soybean oil and shown to be one of the compounds responsible for odor reversion.

The formation of SOA and chemical tracer compounds from the photooxidation of naphthalene and its methyl analogs in the presence and absence of nitrogen oxides

EPA Science Inventory

Laboratory smog chamber experiments have been carried out to investigate secondary organic aerosol (SOA)formation from the photooxidation of naphthalene and its methyl analogs, 1- and 2-methylnaphthalene (1-MN and 2- MN, respectively). Laboratory smog chamber irradiations were co...

Effect of the structure distortion on the high photocatalytic performance of C60/g-C3N4 composite

NASA Astrophysics Data System (ADS)

Ma, Xiaojuan; Li, Xinru; Li, Mengmeng; Ma, Xiangchao; Yu, Lin; Dai, Ying

2017-08-01

C60/g-C3N4 composite was reported experimentally to be of high photocatalytic activity in degrading organics. To investigate the underlying mechanism of high photocatalytic performance, the structural and electronic properties of g-C3N4 monolayers with adsorbing and removing fullerene C60 are studied by means of density functional theory calculations. After 25 possible configurations examination, it is found that C60 prefers to stay upon the ;junction nitrogen; with the carbon atom of fullerene being nearest to monolayers. Correspondingly, a type-I band alignment appears. Our results further demonstrate that the adsorption of C60 can lead to an irreversible structure distortion for g-C3N4 from flat to wrinkle, which plays a crucial role in improving photocatalytic performance other than the separation of carriers at interface due to the formation of type-II heterojunctions as previous report. Compared to flat one, the light absorption of wrinkled structure shows augmented, the valence band maximum shifts towards lower position along with a stronger photo-oxidation capability. Interestingly, the results indicate that the energy, light absorption and band edge all have a particular relationship with wrinkle degree. The work presented here can be helpful to understand the mechanism behind the better photocatalytic performance for C60 modified g-C3N4.

Variation in the thermionic work function of semiconductor powders exposed to electromagnetic radiation

NASA Technical Reports Server (NTRS)

Bourasseau, S.; Martin, J. R.; Juillet, F.; Teichner, S. J.

1977-01-01

The study of the variation of thermoelectronic work function potential of TiO2 in the presence of isobutane shows that this gas is not adsorbed on this solid, in either the presence or the absence of ultraviolet radiation. These results, as well as those obtained in a previous work, lead to the mechanism of the photo-oxidation of isobutane at room temperature, in which excited atomic oxygen is the active species.

Carbon nanotube epoxy nanocomposites: the effects of interfacial modifications on the dynamic mechanical properties of the nanocomposites.

PubMed

Yoonessi, Mitra; Lebrón-Colón, Marisabel; Scheiman, Daniel; Meador, Michael A

2014-10-08

Surface functionalization of pretreated carbon nanotubes (CNT) using aromatic, aliphatic, and aliphatic ether diamines was performed. The pretreatment of the CNT consisted of either acid- or photo-oxidation. The acid treated CNT had a higher initial oxygen content compared to the photo-oxidized CNT and this resulted in a higher density of functionalization. X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA) were used to verify the presence of the oxygenated and amine moieties on the CNT surfaces. Epoxy/0.1 wt % CNT nanocomposites were prepared using the functionalized CNT and the bulk properties of the nanocomposites were examined. Macroscale correlations between the interfacial modification and bulk dynamic mechanical and thermal properties were observed. The amine modified epoxy/CNT nanocomposites exhibited up to a 1.9-fold improvement in storage modulus (G') below the glass transition (Tg) and up to an almost 4-fold increase above the Tg. They also exhibited a 3-10 °C increase in the glass transition temperature. The aromatic diamine surface modified epoxy/CNT nanocomposites resulted in the largest increase in shear moduli below and above the Tg and the largest increase in the Tg. Surface examination of the nanocomposites with scanning electron microscopy (SEM) revealed indications of a greater adhesion of the epoxy resin matrix to the CNT, most likely due to the covalent bonding.

Physical model for the photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenburg, B.M.; Krylov, S.N.; Huang, H.D.

1994-12-31

A model for photo-induced toxicity of PAHs to duckweed was developed. Growth inhibition was described by photochemical reactions between PAHs and a hypothetical group of biomolecules (given the notation G) which are required for growth of the plants. Light activation of PAHs was considered in a two compartment system (water and leaves). The reaction scheme includes: photooxidation of PAHs, partitioning of PAHs into leaves, triplet formation of intact PAHs, photosensitization reactions that consume G, and reaction between photooxidized PAHs and G. The assumptions used in the model are: the rate of PAH photooxidation is slower than the rate of assimilation,more » PAH content in solution is approximately constant over the length of the toxicity test, the fluence rate of actinic radiation is lower in the leaves than in solution, the toxicity of intact PAHs with G in the absence of light is negligible, and the reaction of photooxidized PAHs with G does not require light. The authors then analyzed a series of differential equations that described toxicity. The result was an expression for growth inhibition as a function of the initial concentration of the PAH, the spectral distribution of the light source, the absorption spectrum of the PAH, the quantum yield for formation of triplet state PAH, and the rate of photo-oxidation of the PAH. The expression also includes two complex constants that can be solved by a least squares analysis of the empirical data for growth inhibition. Thus, the model allows a prediction of PAH photo-induced toxicity using only physical parameters of PAHs.« less

Measurement of antiphotooxidative properties of isoquinoline alkaloids using transient thermal lens spectroscopy

NASA Astrophysics Data System (ADS)

Hung, J.; Castillo, J.; Laboren, I.; Rodríguez, M.; Hassegawa, M.

2005-11-01

The antiphotooxidative properties of boldine and chloride berberine were studied by time-resolved thermal lensing technique. These compounds belong to isoquinoline alkaloids possessing interesting biological activity (e.g. antibacterial, antimalarial, antitumor). Antiphotooxidative properties of the alkaloids were studied by mechanism of energy transference between powerful oxidizing agents such as singlet oxygen. Singlet oxygen was produced by energy transfer from chlorophyll-sensitized photooxidation of oil by exposure of high light intensities like laser. The lifetimes of singlet oxygen in dimethylsulfoxide, methanol and water were determined to confirm the assignment of the singlet molecular oxygen O II (1Δ g) in the experiments. In order to understand the effect of the alkaloids on active oxygen species, we carried out in detail an analysis of the thermal lensing signal. It was shown that the alkaloids can act as quenchers of singlet oxygen. To demonstrate the ability of the alkaloids to act efficient singlet oxygen acceptors, we have measured the fluorescence spectra of the studied alkaloids in the presence and in the absence of singlet oxygen. The antiphotooxidative activity of boldine and chloride berberine can be explained by the ability to quench singlet oxygen.

CORONA-INDUCED PHOTOXIDATION OF ALCOHOLS AND HYDROCARBONS OVER TIO2 IN THE ABSENCE OF A UV LIGHT SOURCE - A NOVEL AND ENVIRONMENTALLY FRIENDLY METHOD FOR OXIDATION

EPA Science Inventory

Corona-induced photooxidation is a novel oxidation methodology for the efficient oxidation of alcohols and hydrocarbons utilizing the advantage of both the high oxidizing power of ozone formed in the reactor as well as the photooxidation capability of the UV light generated durin...

ANALYSIS OF SECONDARY ORGANIC AEROSOL COMPOUNDS FROM THE PHOTOOXIDATION OF D-LIMONENE IN THE PRESENCE OF NO X AND THEIR DETECTION IN AMBIENT PM 2.5

EPA Science Inventory

Chemical analysis of secondary organic aerosol (SOA) from the photooxidation of a d-limonene/NOx/air mixture was carried out. SOA, generated in a smog chamber, was collected on Zefluor filters. To determine the structural characteristics of the compounds, the filter sample...

APPLICATION OF SAMPLE PRE-OXIDATION OF ARSENITE IN HUMAN URINE PRIOR TO SPECIATON VIA ON-LINE PHOTO-OXIDATION WITH MEMBRANE HYDRIDE GENRATION AND ICP-MS DETECTION

EPA Science Inventory

A pre-oxidation procedure which converts arsenite (AS(III)) to arsenate (As(VVV)) was investigated in urinary arsenic speciation prior to on-line photo-oxidation hydride-generation with ICP-MS detection. This sample pre-oxidation method eliminates As(III) and As(V) preservation c...

Enhanced ethylene photodegradation performance of g-C3N4-Ag3PO4 composites with direct Z-scheme configuration.

PubMed

Chen, Xuxing; Huang, Xintang; Yi, Zhiguo

2014-12-22

Photocatalytic oxidation of ethylene continues to be a challenge at the frontier of chemistry. In a previous report, a simple Ag3 PO4 semiconductor material was shown to have strong photooxidative properties and efficiently oxidised water and decomposed organics in aqueous solution under visible-light illumination. Herein, its effects on the photo-oxidation of gaseous C2 H4 were investigated by fabricating graphitic C3 N4-Ag3 PO4 composite semiconductors with direct Z-scheme configuration. It was found that both the ethylene photo-oxidative activity and the stability of Ag3 PO4 are considerably improved by fabrication of Z-scheme composites. Moreover, stable C2 H4 photo-oxidation activity could be obtained by treating the composite at 450 °C for 3 h after long-term operation. From the point of view of environmental pollutant cleanup, the present technique avoids the side reaction of oxidising water and will be valuable for further investigations on both Ag3 PO4 and CH degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradation of polyethylene by the thermophilic bacterium Brevibacillus borstelensis.

PubMed

Hadad, D; Geresh, S; Sivan, A

2005-01-01

To select a polyethylene-degrading micro-organism and to study the factors affecting its biodegrading activity. A thermophilic bacterium Brevibaccillus borstelensis strain 707 (isolated from soil) utilized branched low-density polyethylene as the sole carbon source and degraded it. Incubation of polyethylene with B. borstelensis (30 days, 50 degrees C) reduced its gravimetric and molecular weights by 11 and 30% respectively. Brevibaccillus borstelensis also degraded polyethylene in the presence of mannitol. Biodegradation of u.v. photo-oxidized polyethylene increased with increasing irradiation time. Fourier Transform Infra-Red (FTIR) analysis of photo-oxidized polyethylene revealed a reduction in carbonyl groups after incubation with the bacteria. This study demonstrates that polyethylene--considered to be inert--can be biodegraded if the right microbial strain is isolated. Enrichment culture methods were effective for isolating a thermophilic bacterium capable of utilizing polyethylene as the sole carbon and energy source. Maximal biodegradation was obtained in combination with photo-oxidation, which showed that carbonyl residues formed by photo-oxidation play a role in biodegradation. Brevibaccillus borstelensis also degraded the CH2 backbone of nonirradiated polyethylene. Biodegradation of polyethylene by a single bacterial strain contributes to our understanding of the process and the factors affecting polyethylene biodegradation.

Modeling atmospheric mineral aerosol chemistry to predict heterogeneous photooxidation of SO2

NASA Astrophysics Data System (ADS)

Yu, Zechen; Jang, Myoseon; Park, Jiyeon

2017-08-01

The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the absorption-desorption kinetics of SO2 and NOx (partitioning between the gas phase and the multilayer coated dust). The reaction of absorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron-hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 55 % of total sulfate (56 ppb SO2, 290 µg m-3 ATD, and NOx less than 5 ppb). At high NOx ( > 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was suppressed by the competition between NO2 and SO2, which both consume the dust-surface oxidants (OH radicals or ozone).

DETAILED ANALYSIS OF SOA ORIGINATING FROM THE PHOTOOXIDATION OF D-LIMONENE IN THE PRESENCE OF NO X AND UV LIGHT AND ITS IMPLICATION TO AMBIENT PM 2.5

EPA Science Inventory

A detailed analysis was carried out of the aerosol phase originated from the photooxidation of d-limonene in the presence of NO_x and artificial light with the analytical emphasis on the identification of oxygenated organic compounds. The major components included six ...

Chemical and physical transformations of organic aerosol from the photo-oxidation of open biomass burning emissions in an environmental chamber

Treesearch

C. J. Hennigan; M. A. Miracolo; G. J. Engelhart; A. A. May; A. A. Presto; T. Lee; A. P. Sullivan; G. R. McMeeking; H. Coe; C. E. Wold; W.-M. Hao; J. B. Gilman; W. C. Kuster; J. de Gouw; B. A. Schichtel; J. L. Collett; S. M. Kreidenweis; A. L. Robinson

2011-01-01

Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different...

Size Controlled Two-dimensional Co3O4 with Exposure of {111} Plane: Synthesis and Catalytic Properties for Photooxidation of Organics

EPA Science Inventory

The size controlled 2D hexagonal structured Co3O4 with exposure of the {111} plane was fabricated, and the catalytic properties for photooxidation of organics using as-prepared samples were investigated. 2D hexagonal structured Co3O4 with the size of 3 m displays higher photocat...

Photooxidation and its effects on the carboxyl content of dissolved organic matter in two coastal rivers in the southeastern United States.

PubMed

Xie, Huixiang; Zafiriou, Oliver C; Cai, Wei-Jun; Zepp, Richard G; Wang, Yongchen

2004-08-01

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.

Nanoparticles with Embedded Porphyrin Photosensitizers for Photooxidation Reactions and Continuous Oxygen Sensing.

PubMed

Kubát, Pavel; Henke, Petr; Berzediová, Veronika; Štěpánek, Miroslav; Lang, Kamil; Mosinger, Jiří

2017-10-18

We report the synthesis and characterization of sulfonated polystyrene nanoparticles (average diameter 30 ± 14 nm) with encapsulated 5,10,15,20-tetraphenylporphyrin or ionically entangled tetracationic 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin, their photooxidation properties, and the application of singlet oxygen-sensitized delayed fluorescence (SODF) in oxygen sensing. Both types of nanoparticles effectively photogenerated singlet oxygen, O 2 ( 1 Δ g ). The O 2 ( 1 Δ g ) phosphorescence, transient absorption of the porphyrin triplet states, and SODF signals were monitored using time-resolved spectroscopic techniques. The SODF intensity depended on the concentration of the porphyrin photosensitizer and dissolved oxygen and on the temperature. After an initial period (a few microseconds), the kinetics of the SODF process can be approximated as a monoexponential function, and the apparent SODF lifetimes can be correlated with the oxygen concentration. The oxygen sensing based on SODF allowed measurement of the dissolved oxygen in aqueous media in the broad range of oxygen concentrations (0.2-38 mg L -1 ). The ability of both types of nanoparticles to photooxidize external substrates was predicted by the SODF measurements and proven by chemical tests. The relative photooxidation efficacy was highest at a low porphyrin concentration, as indicated by the highest fluorescence quantum yield (Φ F ), and it corresponds with negligible inner filter and self-quenching effects. The photooxidation abilities were sensitive to the influence of temperature on the diffusion and solubility of oxygen in both polystyrene and water media and to the rate constant of the O 2 ( 1 Δ g ) reaction with a substrate. Due to their efficient photogeneration of cytotoxic O 2 ( 1 Δ g ) at physiological temperatures and their oxygen sensing via SODF, both types of nanoparticles are promising candidates for biomedical applications.

Rheological characterization of thermal, thermo-oxidative and photo-oxidative degradation of LDPE

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor Hugo; Wagner, Manfred Hermann

2015-04-01

Rheology has been used to study thermal degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011), thermo-oxidative degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011; V. H. Rolón-Garrido et al., J. Rheol. 57, 105-129, 2013) and photo-oxidative degradation (V. H. Rolón-Garrido and M. H. Wagner, Polym. Degrad. Stab. 99, 136-145, 2014; V. H. Rolón-Garrido and M. H. Wagner, J. Rheol. 58, 199-22 2, 2014; V. H. Rolón-Garrido et al., Polym. Degrad. Stab. 111, 46-54, 2015) of low-density polyethylene (LDPE). This contribution presents the analogies and differences between these types of degradations of LDPE on the linear (by use of van-Gurp Palmen plots) and non-linear viscoelastic properties (by use of the parameters of the MSF model, fmax2 and β), as well as on the failure mode of the samples (through the maximum strain and stress achieved experimentally). In contrast to thermal and thermo-oxidative degradation, the linear viscoelastic properties of photo-oxidated samples were more affected by degradation. In the non-linear regime, for thermal and thermo-oxidative treated samples, the elongational measurements elucidated the role of chain scission and long-chain branching (LCB) formation, while for photo-oxidated LDPE even the competition between chain scission, LCB formation, and gel formation was demonstrated. The failure behavior was found to be determined by a constant maximum strain in thermo-oxidative degradation, if the LDPE has high content in branching points, or in photo-oxidative degraded LDPE, if a considerable portion of gel structure is present. Otherwise, either the maximum strain or stress measured was found to be strain-rate dependent.

Photo-stability and time-resolved photoluminescence study of colloidal CdSe/ZnS quantum dots passivated in Al{sub 2}O{sub 3} using atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Chih-Yi; Mao, Ming-Hua, E-mail: mhmao@ntu.edu.tw; Graduate Institute of Electronics Engineering, National Taiwan University, Taipei 10617, Taiwan

2016-08-28

We report photo-stability enhancement of colloidal CdSe/ZnS quantum dots (QDs) passivated in Al{sub 2}O{sub 3} thin film using the atomic layer deposition (ALD) technique. 62% of the original peak photoluminescence (PL) intensity remained after ALD. The photo-oxidation and photo-induced fluorescence enhancement effects of both the unpassivated and passivated QDs were studied under various conditions, including different excitation sources, power densities, and environment. The unpassivated QDs showed rapid PL degradation under high excitation due to strong photo-oxidation in air while the PL intensity of Al{sub 2}O{sub 3} passivated QDs was found to remain stable. Furthermore, recombination dynamics of the unpassivated andmore » passivated QDs were investigated by time-resolved measurements. The average lifetime of the unpassivated QDs decreases with laser irradiation time due to photo-oxidation. Photo-oxidation creates surface defects which reduces the QD emission intensity and enhances the non-radiative recombination rate. From the comparison of PL decay profiles of the unpassivated and passivated QDs, photo-oxidation-induced surface defects unexpectedly also reduce the radiative recombination rate. The ALD passivation of Al{sub 2}O{sub 3} protects QDs from photo-oxidation and therefore avoids the reduction of radiative recombination rate. Our experimental results demonstrated that passivation of colloidal QDs by ALD is a promising method to well encapsulate QDs to prevent gas permeation and to enhance photo-stability, including the PL intensity and carrier lifetime in air. This is essential for the applications of colloidal QDs in light-emitting devices.« less

Photo-oxidation method using MoS2 nanocluster materials

DOEpatents

Wilcoxon, Jess P.

2001-01-01

A method of photo-oxidizing a hydrocarbon compound is provided by dispersing MoS.sub.2 nanoclusters in a solvent containing a hydrocarbon compound contaminant to form a stable solution mixture and irradiating the mixture to photo-oxide the hydrocarbon compound. Hydrocarbon compounds of interest include aromatic hydrocarbon and chlorinated hydrocarbons. MoS.sub.2 nanoclusters with an average diameter less than approximately 10 nanometers are shown to be effective in decomposing potentially toxic aromatic and chlorinated hydrocarbons, such as phenol, pentachlorophenol, chlorinated biphenols, and chloroform, into relatively non-toxic compounds. The irradiation can occur by exposing the MoS.sub.2 nanoclusters and hydrocarbon compound mixture with visible light. The MoS.sub.2 nanoclusters can be introduced to the toxic hydrocarbons as either a MoS.sub.2 solution or deposited on a support material.

Role of methyl group number on SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2015-11-01

Substitution of methyl groups onto the aromatic ring determines the SOA formation from the aromatic hydrocarbon precursor. This study links the number of methyl groups on the aromatic ring to SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions (HC / NO > 10 ppb C : ppb). Aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests as more methyl groups are attached on the aromatic ring, SOA products from these aromatic hydrocarbons become less oxidized per mass/carbon.

Factors controlling the redox potential of ZnCe6 in an engineered bacterioferritin photochemical 'reaction centre'.

PubMed

Mahboob, Abdullah; Vassiliev, Serguei; Poddutoori, Prashanth K; van der Est, Art; Bruce, Doug

2013-01-01

Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical 'reaction centre' (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics-Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal.

Autophagic-lysosomal dysregulation downstream of cathepsin B inactivation in human skin fibroblasts exposed to UVA

PubMed Central

Lamore, Sarah D.; Wondrak, Georg T.

2014-01-01

Recently, using 2D-DIGE proteomics we have identified cathepsin B as a novel target of UVA in human Hs27 skin fibroblasts. In response to chronic exposure to noncytotoxic doses of UVA (9.9 J/cm2, twice a week, 3 weeks), photooxidative impairment of cathepsin B enzymatic activity occurred with accumulation of autofluorescent aggregates colocalizing with lysosomes, an effect mimicked by pharmacological antagonism of cathepsin B using the selective inhibitor CA074Me. Here, we have further explored the mechanistic involvement of cathepsin B inactivation in UVA-induced autophagic-lysosomal alterations using autophagy-directed PCR expression array analysis as a discovery tool. Consistent with lysosomal expansion, UVA upregulated cellular protein levels of the lysosomal marker glycoprotein Lamp-1, and increased levels of the lipidated autophagosomal membrane constituent LC3-II were detected. UVA did not alter expression of beclin 1 (BECN1), an essential factor for initiation of autophagy, but upregulation of p62 (sequestosome 1, SQSTM1), a selective autophagy substrate, and α-synuclein (SNCA), an autophagic protein substrate and aggresome component, was observed at the mRNA and protein level. Moreover, UVA downregulated transglutaminase-2 (TGM2), an essential enzyme involved in autophagolysosome maturation. Strikingly, UVA effects on Lamp-1, LC3-II, beclin 1, p62, α-synuclein, and transglutaminase-2 were mimicked by CA074Me treatment. Taken together, our data suggest that UVA-induced autophagic-lysosomal alterations occur as a consequence of impaired autophagic flux downstream of cathepsin B inactivation, a novel molecular mechanism potentially involved in UVA-induced skin photodamage. PMID:21773629

Photooxidative removal of the herbicide Acid Blue 9 in the presence of hydrogen peroxide: modeling of the reaction for evaluation of electrical energy per order (E EO).

PubMed

Khataee, Ali R; Khataee, Hamid R

2008-09-01

The present work deals with photooxidative removal of the herbicide, Acid Blue 9 (AB9), in water in the presence of hydrogen peroxide (H2O2) under UV light illumination (30 W). The influence of the basic operational parameters such as amount of H2O2, irradiation time and initial concentration of AB9 on the photodegradation efficiency of the herbicide was investigated. The degradation rate of AB9 was not appreciably high when the photolysis was carried out in the absence of H2O2 and it was negligible in the absence of UV light. The photooxidative removal of the herbicide was found to follow pseudo-first-order kinetic, and hence the figure-of-merit electrical energy per order (E Eo) was considered appropriate for estimating the electrical energy efficiency. A mathematical relation between the apparent reaction rate constant and H2O2 used was applied for prediction of the electricity consumption in the photooxidative removal of AB9. The results indicated that this kinetic model, based on the initial rates of degradation, provided good prediction of the E Eo values for a variety of conditions. The results also indicated that the UV/H2O2 process was appropriate as the effective treatment method for removal of AB9 from the contaminated wastewater.

Photo-oxidation products of α-pinene in coarse, fine and ultrafine aerosol: A new high sensitive HPLC-MS/MS method

NASA Astrophysics Data System (ADS)

Feltracco, Matteo; Barbaro, Elena; Contini, Daniele; Zangrando, Roberta; Toscano, Giuseppa; Battistel, Dario; Barbante, Carlo; Gambaro, Andrea

2018-05-01

Oxidation products of α-pinene represent a fraction of organic matter in the environmental aerosol. α-pinene is one of most abundant monoterpenes released in the atmosphere by plants, located typically in boreal, temperate and tropical forests. This primary compound reacts with atmospheric oxidants, such as O3, O2, OH radicals and NOx, through the major tropospheric degradation pathway for many monoterpenes under typical atmospheric condition. Although several studies identified a series of by-products deriving from the α-pinene photo-oxidation in the atmosphere, such as pinic and cis-pinonic acid, the knowledge of the mechanism of this process is partially still lacking. Thus, the investigation of the distribution of these acids in the different size aerosol particles provides additional information on this regard. The aim of this study is twofold. First, we aim to improve the existing analytical methods for the determination of pinic and cis-pinonic acid in aerosol samples, especially in terms of analytical sensitivity and limits of detection (LOD) and quantification (LOQ). We even attempted to increase the knowledge of the α-pinene photo-oxidation processes by analysing, for the first time, the particle-size distribution up to nanoparticle level of pinic and cis-pinonic acid. The analysis of aerosol samples was carried out via high-performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The instrumental LOD values of cis-pinonic and pinic acid are 1.6 and 1.2 ng L-1 while LOQ values are 5.4 and 4.1 ng L-1, respectively. Samples were collected by MOUDI II™ cascade impactor with twelve cut-sizes, from March to May 2016 in the urban area of Mestre-Venice (Italy). The range concentrations in the aerosol samples were from 0.1 to 0.9 ng m-3 for cis-pinonic acid and from 0.1 to 0.8 ng m-3 for pinic acid.

Methods of Functionalization of Carbon Nanotubes by Photooxidation

NASA Technical Reports Server (NTRS)

Lebron-Colon, Marisabel (Inventor); Meador, Michael A. (Inventor)

2016-01-01

A method of photooxidizing carbon nanotubes, such as single-walled and multi-walled carbon nanotubes. The nanotubes are purified and dispersed in a solvent, such as n-methyl pyrrolidinone or dimethylformamide. A singlet oxygen sensitizer like Rose Bengal is added to the solution. Oxygen gas is continuously supplied while irradiating the solution while irradiating the solution with ultraviolet light to produce singlet oxygen to oxidize the single-walled carbon nanotubes. Advantageously, the method significantly increases the level of oxidation compared with prior art methods.

Arabidopsis dehydroascorbate reductase 1 and 2 modulate redox states of ascorbate-glutathione cycle in the cytosol in response to photooxidative stress.

PubMed

Noshi, Masahiro; Yamada, Hiroki; Hatanaka, Risa; Tanabe, Noriaki; Tamoi, Masahiro; Shigeoka, Shigeru

2017-03-01

Ascorbate and glutathione are indispensable cellular redox buffers and allow plants to acclimate stressful conditions. Arabidopsis contains three functional dehydroascorbate reductases (DHAR1-3), which catalyzes the conversion of dehydroascorbate into its reduced form using glutathione as a reductant. We herein attempted to elucidate the physiological role in DHAR1 and DHAR2 in stress responses. The total DHAR activities in DHAR knockout Arabidopsis plants, dhar1 and dhar2, were 22 and 92%, respectively, that in wild-type leaves. Under high light (HL), the levels of total ascorbate and dehydroascorbate were only reduced and increased, respectively, in dhar1. The oxidation of glutathione under HL was significantly inhibited in both dhar1 and dhar2, while glutathione contents were only enhanced in dhar1. The dhar1 showed stronger visible symptoms than the dhar2 under photooxidative stress conditions. Our results demonstrated a pivotal role of DHAR1 in the modulation of cellular redox states under photooxidative stress.

Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

NASA Astrophysics Data System (ADS)

Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

2017-12-01

Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

PubMed

Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

2016-06-07

Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided.

Enhancing visible light photo-oxidation of water with TiO2 nanowire arrays via cotreatment with H2 and NH3: synergistic effects between Ti3+ and N.

PubMed

Hoang, Son; Berglund, Sean P; Hahn, Nathan T; Bard, Allen J; Mullins, C Buddie

2012-02-29

We report a synergistic effect involving hydrogenation and nitridation cotreatment of TiO(2) nanowire (NW) arrays that improves the water photo-oxidation performance under visible light illumination. The visible light (>420 nm) photocurrent of the cotreated TiO(2) is 0.16 mA/cm(2) and accounts for 41% of the total photocurrent under simulated AM 1.5 G illumination. Electron paramagnetic resonance (EPR) spectroscopy reveals that the concentration of Ti(3+) species in the bulk of the TiO(2) following hydrogenation and nitridation cotreatment is significantly higher than that of the sample treated solely with ammonia. It is believed that the interaction between the N-dopant and Ti(3+) is the key to the extension of the active spectrum and the superior visible light water photo-oxidation activity of the hydrogenation and nitridation cotreated TiO(2) NW arrays. © 2012 American Chemical Society

Spectroscopic detection of halogen bonding resolves dye regeneration in the dye-sensitized solar cell.

PubMed

Parlane, Fraser G L; Mustoe, Chantal; Kellett, Cameron W; Simon, Sarah J; Swords, Wesley B; Meyer, Gerald J; Kennepohl, Pierre; Berlinguette, Curtis P

2017-11-24

The interactions between a surface-adsorbed dye and a soluble redox-active electrolyte species in the dye-sensitized solar cell has a significant impact on the rate of regeneration of photo-oxidized dye molecules and open-circuit voltage of the device. Dyes must therefore be designed to encourage these interfacial interactions, but experimentally resolving how such weak interactions affect electron transfer is challenging. Herein, we use X-ray absorption spectroscopy to confirm halogen bonding can exist at the dye-electrolyte interface. Using a known series of triphenylamine-based dyes bearing halogen substituents geometrically positioned for reaction with halides in solution, halogen bonding was detected only in cases where brominated and iodinated dyes were photo-oxidized. This result implies that weak intermolecular interactions between photo-oxidized dyes and the electrolyte can impact device photovoltages. This result was unexpected considering the low concentration of oxidized dyes (less than 1 in 100,000) under full solar illumination.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

NASA Astrophysics Data System (ADS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile-butadiene-styrene model samples and historical objects.

PubMed

Saviello, Daniela; Pouyet, Emeline; Toniolo, Lucia; Cotte, Marine; Nevin, Austin

2014-09-16

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile-butadiene-styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3×3 μm(2)) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time. Copyright © 2014 Elsevier B.V. All rights reserved.

Cyanidin-3-glucoside and its phenolic acid metabolites attenuate visible light-induced retinal degeneration in vivo via activation of Nrf2/HO-1 pathway and NF-κB suppression.

PubMed

Wang, Yong; Huo, Yazhen; Zhao, Liang; Lu, Feng; Wang, Ou; Yang, Xue; Ji, Baoping; Zhou, Feng

2016-07-01

Cyanidin-3-glucoside (C3G) is a major anthocyanin in berries and a potential nutritional supplement for preventing retinal degeneration. However, the protective mechanism of C3G and its metabolites, protocatechuic acid (PCA) and ferulic acid (FA), remain unclear. The molecular mechanisms of C3G and its metabolites against retinal photooxidative damage in vivo are investigated. Pigmented rabbits were orally administered C3G, PCA, and FA (0.11 mmol/kg/day) for 3 weeks. Electroretinography, histological analysis, and TUNEL assay showed that C3G and its metabolites attenuated retinal cell apoptosis. The expression of oxidative stress markers were upregulated after light exposure but attenuated by C3G and FA, which may be attributed to the elevated secretion and expression of heme oxygenase (HO-1) and nuclear factor erythroid-2 related factor 2 (Nrf2). C3G, PCA, and FA attenuated the secretion or expression of inflammation-related genes; FA suppressed nuclear factor kappa B (NF-κB) activation. The treatments attenuated the light-induced changes on certain apoptotic proteins and angiogenesis-related cytokines. C3G and FA reduced light-induced retinal oxidative stress by activating the Nrf2/HO-1 antioxidant pathway. FA attenuated the light-induced retinal inflammation by suppressing NF-κB activation. C3G and its metabolites attenuated the photooxidation-induced apoptosis and angiogenesis in the retina. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Carbon Dioxide Limitation-Inducible Protein, ColA, Supports the Growth of Synechococcus sp. PCC 7002.

PubMed

Shimakawa, Ginga; Watanabe, Satoru; Miyake, Chikahiro

2017-12-15

A limitation in carbon dioxide (CO₂), which occurs as a result of natural environmental variation, suppresses photosynthesis and has the potential to cause photo-oxidative damage to photosynthetic cells. Oxygenic phototrophs have strategies to alleviate photo-oxidative damage to allow life in present atmospheric CO₂ conditions. However, the mechanisms for CO₂ limitation acclimation are diverse among the various oxygenic phototrophs, and many mechanisms remain to be discovered. In this study, we found that the gene encoding a CO₂ limitation-inducible protein, ColA, is required for the cyanobacterium Synechococcus sp. PCC 7002 (S. 7002) to acclimate to limited CO₂ conditions. An S. 7002 mutant deficient in ColA (Δ colA ) showed lower chlorophyll content, based on the amount of nitrogen, than that in S. 7002 wild-type (WT) under ambient air but not high CO₂ conditions. Both thermoluminescence and protein carbonylation detected in the ambient air grown cells indicated that the lack of ColA promotes oxidative stress in S. 7002. Alterations in the photosynthetic O₂ evolution rate and relative electron transport rate in the short-term response, within an hour, to CO₂ limitation were the same between the WT and Δ colA . Conversely, these photosynthetic parameters were mostly lower in the long-term response of a few days in Δ colA than in the WT. These data suggest that ColA is required to sustain photosynthetic activity for living under ambient air in S. 7002. The unique phylogeny of ColA revealed diverse strategies to acclimate to CO₂ limitation among cyanobacteria.

Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons.

PubMed

Ng, Nga L; Kroll, Jesse H; Keywood, Melita D; Bahreini, Roya; Varutbangkul, Varuntida; Flagan, Richard C; Seinfeld, John H; Lee, Anita; Goldstein, Allen H

2006-04-01

Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase concentrations (monitored by a Proton Transfer Reaction Mass Spectrometer, PTR-MS), we study the general mechanisms of SOA formation. Aerosol growth data are presented in terms of a "growth curve", a plot of aerosol mass formed versus the amount of hydrocarbon reacted. From the shapes of the growth curves, it is found that all the hydrocarbons studied can be classified into two groups based entirely on the number of double bonds of the hydrocarbon, regardless of the reaction systems (ozonolysis or photooxidation) and the types of hydrocarbons studied: compounds with only one double bond and compounds with more than one double bond. For compounds with only one double bond, the first oxidation step is rate-limiting, and aerosols are formed mainly from low volatility first-generation oxidation products; whereas for compounds with more than one double bond, the second oxidation step may also be rate-limiting and second-generation products contribute substantially to SOA growth. This behavior is characterized by a vertical section in the growth curve, in which continued aerosol growth is observed even after all the parent hydrocarbon is consumed.

Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

NASA Astrophysics Data System (ADS)

Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

2011-09-01

A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CNmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = -0.5 - 0).

Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

NASA Astrophysics Data System (ADS)

Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

2012-01-01

A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = -0.5-0).

Substrate specificity and kinetic properties of alpha-galactosidases from Vicia faba.

PubMed

Dey, P M; Pridham, J B

1969-10-01

1. The hydrolysis of a variety of galactosides and other glycosides by alpha-galactosidases I and II of Vicia faba was studied. 2. The effect of temperature on kinetic parameters was also examined. 3. Both enzymes are inhibited by excess of substrate (p-nitrophenyl alpha-d-galactoside); with enzyme I this is competitive and is caused by the galactosyl moiety. 4. Enzyme I is inhibited by oligosaccharides possessing terminal non-reducing galactose residues and to a smaller extent by l-arabinose and d-fucose. 5. The effect of pH on K(m) and V(max.) values suggests that carboxyl and imidazole groups are involved in the catalytic activity of enzyme I. 6. Photo-oxidation experiments with enzyme I also suggest that an imidazole group is present at the active site.

Photosynthetic response to low sink demand after fruit removal in relation to photoinhibition and photoprotection in peach trees.

PubMed

Duan, Wei; Fan, Pei G; Wang, Li J; Li, Wei D; Yan, Shu T; Li, Shao H

2008-01-01

Diurnal variations in photosynthesis, chlorophyll fluorescence, xanthophyll cycle, antioxidant enzymes and antioxidant metabolism in leaves in response to low sink demand caused by fruit removal (-fruit) were studied in 'Zaojiubao' peach (Prunus persica (L.) Batch) trees during the final stage of rapid fruit growth. Compared with the retained fruit treatment (+fruit), the -fruit treatment resulted in a significantly lower photosynthetic rate, stomatal conductance and transpiration rate, but generally higher internal CO(2) concentration, leaf-to-air vapor pressure difference and leaf temperature. The low photosynthetic rate in the -fruit trees paralleled reductions in maximal efficiency of photosystem II (PSII) photochemistry and carboxylation efficiency. The midday depression in photosynthetic rate in response to low sink demand resulting from fruit removal was mainly caused by non-stomatal limitation. Fruit removal resulted in lower quantum efficiency of PSII as a result of both a decrease in the efficiency of excitation capture by open PSII reaction centers and an increase in closure of PSII reaction centers. Both xanthophyll-dependent thermal dissipation and the antioxidant system were up-regulated providing protection from photo-oxidative damage to leaves during low sink demand. Compared with the leaves of +fruit trees, leaves of -fruit trees had a larger xanthophyll cycle pool size and a higher de-epoxidation state, as well as significantly higher activities of antioxidant enzymes, including superoxide dismutase, ascorbate peroxidase, monodehydroascorbate reductase, dehydroascorbate reductase, glutathione reductase and a higher reduction state of ascorbate and glutathione. However, the -fruit treatment resulted in higher hydrogen peroxide and malondialdehyde concentrations compared with the +fruit treatment, indicating photo-oxidative damage.

Flow injection chemiluminescence determination of vitamin B12 using on-line UV-persulfate photooxidation and charge coupled device detection.

PubMed

Murillo Pulgarín, José A; García Bermejo, Luisa F; Sánchez García, M Nieves

2011-01-01

A sensitive chemiluminescence method for vitamin B(12) using a charge-coupled device (CCD) photodetector combined with on-line UV-persulfate oxidation in a simple continuous flow system has been developed. The principle for the determination of vitamin B(12) is based on the enhancive effect of cobalt (II) on the chemiluminescence reaction between luminol and percarbonate in alkaline medium. In addition, percarbonate has been investigated and proposed as a powerful source of hydrogen peroxide as oxidant agent in this chemiluminescence reaction. The digestion of vitamin B(12) to release the cobalt (II) is reached by UV irradiation treatment in a persulfate medium. The CCD detector, directly connected to the flow cell, is used with the continuous flow manifold to obtain the full spectral characteristics of cobalt (II) catalyzed luminol-percarbonate reaction. The vitamin B(12) oxidation process and chemical conditions for the chemiluminescence reaction were investigated and optimized. The increment of the emission intensity was proportional to the concentration of vitamin B(12) , giving a second-order calibration graph over the cobalt (II) concentration range from 10 to 5000 μg L(-1)(r(2) = 0.9985) with a detection limit of 9.3 μg L(-1). The proposed method was applied to the determination of vitamin B(12) in different kinds of pharmaceuticals. Copyright © 2011 John Wiley & Sons, Ltd.

The Antisense RNA As1_flv4 in the Cyanobacterium Synechocystis sp. PCC 6803 Prevents Premature Expression of the flv4-2 Operon upon Shift in Inorganic Carbon Supply*

PubMed Central

Eisenhut, Marion; Georg, Jens; Klähn, Stephan; Sakurai, Isamu; Mustila, Henna; Zhang, Pengpeng; Hess, Wolfgang R.; Aro, Eva-Mari

2012-01-01

The functional relevance of natural cis-antisense transcripts is mostly unknown. Here we have characterized the association of three antisense RNAs and one intergenically encoded noncoding RNA with an operon that plays a crucial role in photoprotection of photosystem II under low carbon conditions in the cyanobacterium Synechocystis sp. PCC 6803. Cyanobacteria show strong gene expression dynamics in response to a shift of cells from high carbon to low levels of inorganic carbon (Ci), but the regulatory mechanisms are poorly understood. Among the most up-regulated genes in Synechocystis are flv4, sll0218, and flv2, which are organized in the flv4-2 operon. The flavodiiron proteins encoded by this operon open up an alternative electron transfer route, likely starting from the QB site in photosystem II, under photooxidative stress conditions. Our expression analysis of cells shifted from high carbon to low carbon demonstrated an inversely correlated transcript accumulation of the flv4-2 operon mRNA and one antisense RNA to flv4, designated as As1_flv4. Overexpression of As1_flv4 led to a decrease in flv4-2 mRNA. The promoter activity of as1_flv4 was transiently stimulated by Ci limitation and negatively regulated by the AbrB-like transcription regulator Sll0822, whereas the flv4-2 operon was positively regulated by the transcription factor NdhR. The results indicate that the tightly regulated antisense RNA As1_flv4 establishes a transient threshold for flv4-2 expression in the early phase after a change in Ci conditions. Thus, it prevents unfavorable synthesis of the proteins from the flv4-2 operon. PMID:22854963

Diurnal and Seasonal Responses of High Frequency Chlorophyll Fluorescence and PRI Measurements to Abiotic Stress in Almonds

NASA Astrophysics Data System (ADS)

Bambach-Ortiz, N. E.; Paw U, K. T.

2016-12-01

Plants have evolved to efficiently utilize light to synthesize energy-rich carbon compounds, and at the same time, dissipate absorbed but excessive photon that would otherwise transfer excitation energy to potentially toxic reactive oxygen species (ROS). Nevertheless, even the most rapidly growing plants with the highest rates of photosynthesis only utilize about half of the light their leaves absorb during the hours of peak irradiance in sun-exposed habitats. Usually, that daily peak of irradiance coincides with high temperature and a high vapor pressure deficit, which are conditions related to plant stomata closure. Consequently, specially in water stressed environments, plants need to have mechanisms to dissipate most of absorbed photons. Plants avoid photo-oxidative damage of the photosynthetic apparatus due to the formation of ROS under excess light using different mechanisms in order to either lower the amount of ROS formation or detoxify already formed ROS. Photoinhibition is defined as a reduction in photosynthetic activity due largely to a sustained reduction in the photochemical efficiency of Photosystem II (PSII), which can be assessed by monitoring Chlorophyll a fluorescence (ChlF). Alternatively, monitoring abiotic stress effects upon photosynthetic activity and photoinhibition may be possible using high frequency spectral reflectance sensors. We aim to find the potential relationships between high frequency PRI and ChlF as indicators of photoinhibition and permanent photodamage at a seasonal scale. Preliminary results show that PRI responses are sensitive to photoinhibition, but provide a poor representation of permanent photodamage observed at a seasonal scale.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Saewung

The University of California, Irvine, science team (Dr. Saewung Kim, Dr. Roger Seco, Dr. Alex Guenther, and Dr. Jim Smith) deployed a chemical ionization mass spectrometer system for hydroxyl radical (OH) and sulfuric acid quantifications. As part of the GoAmazon 2014/15 field campaign. Hydroxyl radical determines tropospheric oxidation capacity and had been expected to be very low in the pristine rain forest region such as the Brazilian Amazon because of the presence of significant levels of highly reactive biogenic volatile organic compounds and very low levels of NO, which is an OH recycling agent. However, several recent in situ OHmore » observations provided by a laser-induced fluorescence system reported unaccountably high OH concentrations. To address this discrepancy, a series of laboratory and theoretical studies has postulated chemical reaction mechanisms of isoprene that may regenerate OH in photo-oxidation processes. Along with these efforts, potential artifacts on the laser induced fluorescence system from isoprene and its oxidation products also have been explored. Therefore, the first chemical ionization mass spectrometer observations at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s T3 site in Manacapuru, Brazil, are expected to provide a critical experimental constraint to address uncertainty in constraining oxidation capacity over pristine rain forest environments. In addition, we deployed a National Center for Atmospheric Research (NCAR) proton transfer reaction time-of-flight mass spectrometer to characterize atmospheric volatile organic compound levels, especially isoprene and its oxidation products, which are critical input parameters for box modeling to simulate OH with different isoprene photo-oxidation schemes. As there has been no report on noticeable new particle formation events, our first in situ sulfuric acid observations in the Amazon rain forest were expected to constrain the reasons behind such observations. The planned field observations during Intensive Observational Periods I and II, post-field campaign calibrations, and preliminary data reports have been completed. We presented preliminary data analysis results at the 2014 American Geophysical Union Fall meeting and the GOAmazon Science Meeting in Boston (May 2015). We are in the process of submitting two more abstracts to the 2015 American Geophysical Union fall meeting while we are preparing two manuscripts to be submitted to (tentatively) the GOAmazon special issue of Atmospheric Chemistry and Physics.« less

Photo-Oxidation Products of Skin Surface Squalene Mediate Metabolic and Inflammatory Responses to Solar UV in Human Keratinocytes

PubMed Central

Kostyuk, Vladimir; Potapovich, Alla; Stancato, Andrea; De Luca, Chiara; Lulli, Daniela; Pastore, Saveria; Korkina, Liudmila

2012-01-01

The study aimed to identify endogenous lipid mediators of metabolic and inflammatory responses of human keratinocytes to solar UV irradiation. Physiologically relevant doses of solar simulated UVA+UVB were applied to human skin surface lipids (SSL) or to primary cultures of normal human epidermal keratinocytes (NHEK). The decay of photo-sensitive lipid-soluble components, alpha-tocopherol, squalene (Sq), and cholesterol in SSL was analysed and products of squalene photo-oxidation (SqPx) were quantitatively isolated from irradiated SSL. When administered directly to NHEK, low-dose solar UVA+UVB induced time-dependent inflammatory and metabolic responses. To mimic UVA+UVB action, NHEK were exposed to intact or photo-oxidised SSL, Sq or SqPx, 4-hydroxy-2-nonenal (4-HNE), and the product of tryptophan photo-oxidation 6-formylindolo[3,2-b]carbazole (FICZ). FICZ activated exclusively metabolic responses characteristic for UV, i.e. the aryl hydrocarbon receptor (AhR) machinery and downstream CYP1A1/CYP1B1 gene expression, while 4-HNE slightly stimulated inflammatory UV markers IL-6, COX-2, and iNOS genes. On contrast, SqPx induced the majority of metabolic and inflammatory responses characteristic for UVA+UVB, acting via AhR, EGFR, and G-protein-coupled arachidonic acid receptor (G2A). Conclusions/Significance Our findings indicate that Sq could be a primary sensor of solar UV irradiation in human SSL, and products of its photo-oxidation mediate/induce metabolic and inflammatory responses of keratinocytes to UVA+UVB, which could be relevant for skin inflammation in the sun-exposed oily skin. PMID:22952984

Bidirectional Photoinduced Electron Transfer in Ruthenium(II)-Tris-bipyridyl-Modified PpcA, a Multi-heme c -Type Cytochrome from Geobacter sulfurreducens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kokhan, Oleksandr; Ponomarenko, Nina S.; Pokkuluri, P. Raj

PpcA, a tri-heme cytochrome c7 from Geobacter sulfurreducens was investigated as a model for photosensitizer-initiated electron transfer within a multi-heme "molecular wire" protein architecture. E. coli expression of PpcA was found to be tolerant of cysteine site-directed mutagenesis, demonstrated by the successful expression of natively folded proteins bearing cysteine mutations at a series of sites selected to vary characteristically with respect to the three -CXXCH- heme binding domains. A preliminary survey of 5 selected mutants found that the introduced cysteines can be readily covalently linked to a Ru(II)-(2,2'-bpy)2(4-bromomethyl-4’-methyl-2,2'-bpy) photosensitizer (where bpy = bipyridine), and that the linked constructs support bothmore » photo-oxidative and photo-reductive quenching of the photosensitizer excited-state, depending upon the initial heme redox state. For photo-oxidative electron transfer, apparent heme reduction risetimes were found to vary from 7 x 10-12 s to 5 x 10-8 s, depending upon the site of photosensitizer linking. The excited-state electron transfers are about 103-fold faster than any previously reported photosensitizer-redox protein covalently linked construct. Preliminary conformational analysis using molecular dynamics simulations shows that rates for electron transfer track both the distance and pathways for electron transfer. Two mutants with the fastest charge transfer rates, A23C and K29C, showed a significant role of specific paths for electron transfer. While K29C labeled mutant was expected to have approximately 0.8Å greater donor-acceptor distance, it showed 20-fold faster charge separation rate. Clear evidence for inter-heme electron transfer within the multi-heme protein is not detected within the lifetimes of the charge separated states. These results demonstrate an opportunity to develop multi-heme c-cytochromes for investigation of electron transfer in protein "molecular wires" and to serve as frameworks for metalloprotein designs that support multiple electron transfer redox chemistry.« less

High-NOx Photooxidation of n-Dodecane: Temperature Dependence of SOA Formation.

PubMed

Lamkaddam, Houssni; Gratien, Aline; Pangui, Edouard; Cazaunau, Mathieu; Picquet-Varrault, Bénédicte; Doussin, Jean-François

2017-01-03

The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (C 12 H 26 ) in the presence of NO x in the CESAM chamber (French acronym for "Chamber for Atmospheric Multiphase Experimental Simulation"). Experiments were performed with and without seed aerosol between 283 and 304.5 K. In order to quantify the SOA yields, a new parametrization is proposed to account for organic vapor loss to the chamber walls. Deposition processes were found to impact the aerosol yields by a factor from 1.3 to 1.8 between the lowest and the highest value. As with other photooxidation systems, experiments performed without seed and at low concentration of oxidant showed a lower SOA yield than other seeded experiments. Temperature did not significantly influence SOA formation in this study. This unforeseen behavior indicates that the SOA is dominated by sufficiently low volatility products for which a change in their partitioning due to temperature would not significantly affect the condensed quantities.

Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu

2014-04-08

Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and inmore » ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.« less

Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

2013-12-01

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under supersaturated O2 initial conditions).

Reliability and engineering sciences area. Materials research: Single junction thin film

NASA Technical Reports Server (NTRS)

1986-01-01

A test bench was designed and fabricated for the purpose of improving control of hot-spot test accuracy. Electrochemical corrosion research focused on corrosion mechanisms to which both crystalline and a-Si modules may be subjected in central station applications. A variety of cells and several designs were subjected to accelerated stress tests. Humiditiy degradation rates were determined and key electrochemical failure mechanisms were identified. Software was developed for the prediction of power loss resulting from open circuits in an array field of a-Si modules. Failure analysis was continued on the four ARCO Solar Genesis modules. The interactions of water on the silicon module was examined. An autocatalytic photooxidation model was proposed. The reliability and durability of bonding materials and electrical insulation were also studied.

A Carbon Dioxide Limitation-Inducible Protein, ColA, Supports the Growth of Synechococcus sp. PCC 7002

PubMed Central

Shimakawa, Ginga; Watanabe, Satoru; Miyake, Chikahiro

2017-01-01

A limitation in carbon dioxide (CO2), which occurs as a result of natural environmental variation, suppresses photosynthesis and has the potential to cause photo-oxidative damage to photosynthetic cells. Oxygenic phototrophs have strategies to alleviate photo-oxidative damage to allow life in present atmospheric CO2 conditions. However, the mechanisms for CO2 limitation acclimation are diverse among the various oxygenic phototrophs, and many mechanisms remain to be discovered. In this study, we found that the gene encoding a CO2 limitation-inducible protein, ColA, is required for the cyanobacterium Synechococcus sp. PCC 7002 (S. 7002) to acclimate to limited CO2 conditions. An S. 7002 mutant deficient in ColA (ΔcolA) showed lower chlorophyll content, based on the amount of nitrogen, than that in S. 7002 wild-type (WT) under ambient air but not high CO2 conditions. Both thermoluminescence and protein carbonylation detected in the ambient air grown cells indicated that the lack of ColA promotes oxidative stress in S. 7002. Alterations in the photosynthetic O2 evolution rate and relative electron transport rate in the short-term response, within an hour, to CO2 limitation were the same between the WT and ΔcolA. Conversely, these photosynthetic parameters were mostly lower in the long-term response of a few days in ΔcolA than in the WT. These data suggest that ColA is required to sustain photosynthetic activity for living under ambient air in S. 7002. The unique phylogeny of ColA revealed diverse strategies to acclimate to CO2 limitation among cyanobacteria. PMID:29244744

The chloroplast NADPH thioredoxin reductase C, NTRC, controls non-photochemical quenching of light energy and photosynthetic electron transport in Arabidopsis.

PubMed

Naranjo, Belén; Mignée, Clara; Krieger-Liszkay, Anja; Hornero-Méndez, Dámaso; Gallardo-Guerrero, Lourdes; Cejudo, Francisco Javier; Lindahl, Marika

2016-04-01

High irradiances may lead to photooxidative stress in plants, and non-photochemical quenching (NPQ) contributes to protection against excess excitation. One of the NPQ mechanisms, qE, involves thermal dissipation of the light energy captured. Importantly, plants need to tune down qE under light-limiting conditions for efficient utilization of the available quanta. Considering the possible redox control of responses to excess light implying enzymes, such as thioredoxins, we have studied the role of the NADPH thioredoxin reductase C (NTRC). Whereas Arabidopsis thaliana plants lacking NTRC tolerate high light intensities, these plants display drastically elevated qE, have larger trans-thylakoid ΔpH and have 10-fold higher zeaxanthin levels under low and medium light intensities, leading to extremely low linear electron transport rates. To test the impact of the high qE on plant growth, we generated an ntrc-psbs double-knockout mutant, which is devoid of qE. This double mutant grows faster than the ntrc mutant and has a higher chlorophyll content. The photosystem II activity is partially restored in the ntrc-psbs mutant, and linear electron transport rates under low and medium light intensities are twice as high as compared with plants lacking ntrc alone. These data uncover a new role for NTRC in the control of photosynthetic yield. © 2015 John Wiley & Sons Ltd.

Tocopherol-deficient rice plants display increased sensitivity to photooxidative stress.

PubMed

Chen, Defu; Chen, Haiwei; Zhang, Luhua; Shi, Xiaoli; Chen, Xiwen

2014-06-01

Tocopherols are lipophilic antioxidants that are synthesized exclusively in photosynthetic organisms. Despite extensive in vivo characterization of tocopherol functions in plants, their functions in the monocot model plant, rice, remain to be determined. In this study, transgenic rice plants constitutively silenced for homogentisate phytyltransferase (HPT) and tocopherol cyclase (TC) activity were generated. Silencing of HPT and TC resulted in up to a 98 % reduction in foliar tocopherol content relative to the control plants, which was also confirmed by transcript level analysis. When grown under normal conditions, HPT and TC transgenics showed no distinctive phenotype relative to the control plants, except a slight reduction in plant height and a slight decrease in the first leaf length. However, when exposed to high light at low temperatures, HPT and TC transgenics had a significantly higher leaf yellowing index than the control plants. The tocopherol-deficient plants decreased their total individual chlorophyll levels, their chlorophyll a/b ratio, and the maximum photochemical efficiency of photosystem II, whereas increased lipid peroxidation levels relative to the control plants. Tocopherol deficiency had no effect on ascorbate biosynthesis, but induced glutathione, antheraxanthin, and particularly zeaxanthin biosynthesis for compensation under stressful conditions. However, despite these compensation mechanisms, HPT and TC transgenics still exhibited altered phenotypes under high light at low temperatures. Therefore, it is suggested that tocopherols cannot be replaced and play an indispensable role in photoprotection in rice.

Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2016-02-01

Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO > 10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.

Gas-phase and particulate products from the atmospheric degradation of the organothiophosphorus insecticide chlorpyrifos-methyl.

PubMed

Borrás, Esther; Tortajada-Genaro, Luis Antonio; Ródenas, Milagros; Vera, Teresa; Coscollá, Clara; Yusá, Vicent; Muñoz, Amalia

2015-11-01

The phosphorothioate structure is highly present in several organophosphorus pesticides. However, there is insufficient information about its degradation process after the release to the atmosphere and the secondary pollutants formed. Herein, the atmospheric reaction of chlorpyrifos-methyl (o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate), is described for semi-urban or rural locations. The photo-oxidation under low NOx conditions (5-55 ppbV) was reproduced in a large outdoor simulation chamber, observing a rapid degradation (lifetime<3.5 h). The formation of gaseous products and particulate matter (aerosol yield 2-8%) was monitored. The chemical composition of minor products (gaseous and particulate) was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate, dimethyl 3,5,6-trichloropyridin-2-yl phosphate, o-methyl o-(3,5,6-trichloropyridin-2-yl) hydrogen phosphorothioate, 3,5,6-trichloropyridin-2-yl dihydrogen phosphate, 3,5,6-trichloropyridin-2-ol, and 3,5,6-trichloropyridine-2,4-diol. An atmospheric degradation mechanism has been proposed based on an oxidation started with OH-nucleophilic attack to P=S bond. The results have been extrapolated to other organothiophosphorus molecules, such as malathion, parathion, diazinon and methidathion, among many others, to estimate their photo-oxidative degradation and the expected products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sunlight Controls Water Column Processing of Carbon in Arctic Freshwaters

NASA Astrophysics Data System (ADS)

Cory, R. M.; Ward, C. P.; Crump, B. C.; Kling, G. W.

2014-12-01

Carbon (C) in thawing permafrost soils may have global impacts on climate change, yet controls on its processing and fate are poorly understood. The dominant fate of dissolved organic C (DOC) released from soils to inland waters is either complete oxidation to CO2 or partial oxidation and river export to oceans. Both processes are most often attributed to bacterial respiration, but we recently showed that photochemical oxidation exceeds rates of respiration and accounts for 70-95% of total DOC processed in the water column of arctic lakes and rivers. While the overall dominance of photochemical processing in streams and lakes remained, the fate of DOC varied consistently by water type. In small streams DOC was mainly mineralized by sunlight to CO2, while in lakes the main fate of DOC was partial photo-oxidation. Large rivers were intermediate between these end members, and photo-mineralization to CO2 was about equal to or less than partial photo-oxidation. We suggest this pattern is a result of light-exposure history, where DOC leached from soils into headwater streams has little prior light exposure and is labile to complete photo-oxidation, but as light exposure increases moving downstream and into lakes with longer residence times the DOC photo-lability declines. Thus as easily photo-mineralized moieties are removed, DOC fate shifts toward partial photo-oxidation and downstream export in rivers and lakes. At the basin scale, photochemical processing of DOC is about one third of the total CO2 released from surface waters, and is thus an important, newly measured component of the Arctic C budget. We also suggest that these photochemical transformations of DOC will occur in any shallow surface water, and could be important for better understanding inland water carbon cycling.

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ono, Y., E-mail: ono-y@kanagawa-iri.go.jp; Rachi, T.; Yokouchi, M.

2013-06-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO{sub 2}/apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO{sub 2})/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acidmore » concentration, the TiO{sub 2}/HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO{sub 2} particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO{sub 2} powder, Degussa P25. The highest rate was obtained in the TiO{sub 2}/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO{sub 2} photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO{sub 2}/HAp composites compared with the TiO{sub 2} powders.« less

Combating photooxidative stress in green hairy roots of Daucus carota cultivated under light irradiation.

PubMed

Mukherjee, Chiranjit; Sircar, Debabrata; Chatterjee, Moniya; Das, Sampa; Mitra, Adinpunya

2014-01-15

The light-dependent generation of active oxygen species, which can disrupt normal metabolic process of plant, is termed as photo-oxidative stress. Plants are equipped with enzymatic and non-enzymatic antioxidative defence system to reduce the effect of such stress. Hairy root culture of Daucus carota when cultivated under continuous illumination (250 μmol m(-2)s(-1)) turned green. To know the reason behind that and photo-oxidative stress response in green hairy roots, activities of several antioxidant enzymes were measured. When compared with normal hairy roots, green hairy roots showed an enhanced superoxide dismutase (SOD) activity. Treatment with a SOD inhibitor diethyldithiocarbamate led to suppression of SOD activity in a concentration-dependent manner in green hairy roots. Interestingly, SOD-suppressed root showed three-fold enhanced caffeic acid glucoside accumulation in the soluble fraction as compared to untreated ones. While ascorbate peroxidase activity showed marginal increase in green hairy roots, a decrease in the activities of guaiacol peroxidase and catalase were observed. SDS-PAGE of crude protein profile from green hairy roots showed a distinct band, which was absent in normal hairy roots. MALDI-TOF-MS/MS analysis of the extracted protein confirmed it as the large subunit of RuBisCO. RT-PCR based expression analysis of betaine aldehyde dehydrogenase showed enhanced transcript levels in green hairy roots as compared to normal hairy roots, whereas reverse trends were observed with the transcripts accumulation for phenylalanine ammonia-lyase and chalcone synthase. These findings corroborate with the in vitro BADH activities in hairy roots, and thus indicate an important role of this stress enzyme in combating photo-oxidative stress in green hairy roots upon continuous light exposure. Copyright © 2013 Elsevier GmbH. All rights reserved.

Protein Characterization of Javan Cobra (Naja sputatrix) Venom Following Sun Exposure and Photo-Oxidation Treatment

NASA Astrophysics Data System (ADS)

Sulistiyani; Biki, R. S.; Andrianto, D.

2017-03-01

Snake venom has always been known for its toxicity that can cause fatality, however, it is also one of the important biological resources to be used for disease treatment. In Indonesia, snake venom previously expose under the sun has been used for alternative treatment of some diseases such as dengue fever, atherosclerosis, cancer, and diabetes. There has been very little scientific evidence on the use of snake venom of Indonesia origin as well as its protein characteristic. Thus, the objective of this research is to characterize the protein content and the specific activity of the venom of Javan Cobra (N.sputatrix) when treated with sun exposure in comparison with photo-oxidation by ultraviolet. Qualitative analysis of protein contents was determined using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE). The L-amino acid oxidase activity (LAAO) and the phospholipase A2 (PLA2) activities were determined using spectrophotometry. The venom’s protein was separated into 5 main protein bands with molecular weight ranging from 14 to 108 kDa. A time course study showed that the venom lost 91% of its LAAO activity and 96% of PLA2 activity after 6 hours of sun exposure. UV photo-oxidation carried out for 3 hours decreased 91% of LAAO activity, and almost diminished all of PLA2 activity (99.8%). These findings suggest that the exposure of N. sputatrix venom under the sun and UV photo-oxidation decreased its toxicity as shown by the significant reduction of the enzymes activity, but did not affect the protein’s integrity. Therefore, these approaches produced N.sputatrix venom with less toxicity but still withheld other characters of intact proteins.

Relating the Chemical Composition of Dissolved Organic Matter Draining Permafrost Soils to its Photochemical Degradation in Arctic Surface Waters.

NASA Astrophysics Data System (ADS)

Ward, C.; Cory, R. M.

2015-12-01

Thawing permafrost soils are expected to shift the chemical composition of DOM exported to and degraded in arctic surface waters. While DOM photo-degradation is an important component of the freshwater C cycle in the Arctic, the molecular controls on DOM photo-degradation remain poorly understood, making it difficult to predict how shifting chemical composition may alter DOM photo-degradation in arctic surface waters. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer to complete photo-oxidation to CO₂ and partial photo-oxidation to compounds that remain in the DOM pool, and investigated changes in DOM chemical composition following sunlight exposure. DOM leached from the organic mat contained higher molecular weight, more oxidized and unsaturated aromatic species compared to permafrost DOM. Despite significant differences in initial chemical composition, permafrost and organic mat DOM had similar susceptibilities to complete photo-oxidation to CO₂. Concurrent losses of carboxyl moieties and shifts in chemical composition during photo-degradation indicated that carboxyl-rich tannin-like compounds in both DOM sources were likely photo-decarboxylated to CO₂. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic compounds that act as "antioxidants" and slow the oxidation of DOM. These results demonstrated how chemical composition controls the photo-degradation of DOM in arctic surface waters, and that DOM photo-degradation will likely remain an important component of the freshwater C budget in the Arctic with increased export of permafrost DOM to surface waters.

Evolution of Vision

NASA Astrophysics Data System (ADS)

Ostrovsky, Mikhail

The evolution of photoreception, giving rise to eye, offers a kaleidoscopic view on selection acting at both the organ and molecular levels. The molecular level is mainly considered in the lecture. The greatest progress to date has been made in relation to the opsin visual pigments. Opsins appeared before eyes did. Two- and three-dimensional organization for rhodopsin in the rod outer segment disk membrane, as well as molecular mechanisms of visual pigments spectral tuning, photoisomerization and also opsin as a G-protein coupled receptor are considered. Molecular mechanisms of visual pigments spectral tuning, namely switching of chromophore (physiological time scale) and amino acid changes in the chromophore site of opsin (evolutionary time scale) is considered in the lecture. Photoisomerization of rhodopsin chromophore, 11-cis retinal is the only photochemical reaction in vision. The reaction is extemely fast (less that 200 fs) and high efficient (. is 0.65). The rhodopsin photolysis and kinetics of the earlier products appearance, photo- and bathorhodopsin, is considered. It is known that light is not only a carrier of information, but also a risk factor of damage to the eye. This photobiological paradox of vision is mainly due to the nature of rhodopsin chromophore. Photooxidation is the base of the paradox. All factors present in the phototrceptor cells to initiate free-radical photooxidation: photosensitizers, oxygen and substrates of oxidation: lipids and proteins (opsin). That is why photoprotective system of the eye structures appeared in the course of evolution. Three lines of protective system to prevent light damage to the retina and retina pigment epithelium is known: permanent renewal of rod and cone outer segment, powerful antioxidant system and optical media as cut-off filters where the lens is a key component. The molecular mechanisms of light damage to the eye and photoprotective system of the eye is considered in the lecture. The molecular mechanisms of phototransduction in vertebrates eye is also briefly considered in the lecture. Evolution of vision is an enormous subject for thought and investigation. In the postgenomic era evolutionary molecular physiology as a whole and evolutionary molecular physiology of vision can be considered as a key approach for understanding how genome is working.

The knockdown of chloroplastic ascorbate peroxidases reveals its regulatory role in the photosynthesis and protection under photo-oxidative stress in rice.

PubMed

Caverzan, Andréia; Bonifacio, Aurenivia; Carvalho, Fabricio E L; Andrade, Claudia M B; Passaia, Gisele; Schünemann, Mariana; Maraschin, Felipe Dos Santos; Martins, Marcio O; Teixeira, Felipe K; Rauber, Rafael; Margis, Rogério; Silveira, Joaquim Albenisio Gomes; Margis-Pinheiro, Márcia

2014-01-01

The inactivation of the chloroplast ascorbate peroxidases (chlAPXs) has been thought to limit the efficiency of the water-water cycle and photo-oxidative protection under stress conditions. In this study, we have generated double knockdown rice (Oryza sativa L.) plants in both OsAPX7 (sAPX) and OsAPX8 (tAPX) genes, which encode chloroplastic APXs (chlAPXs). By employing an integrated approach involving gene expression, proteomics, biochemical and physiological analyses of photosynthesis, we have assessed the role of chlAPXs in the regulation of the protection of the photosystem II (PSII) activity and CO2 assimilation in rice plants exposed to high light (HL) and methyl violagen (MV). The chlAPX knockdown plants were affected more severely than the non-transformed (NT) plants in the activity and structure of PSII and CO2 assimilation in the presence of MV. Although MV induced significant increases in pigment content in the knockdown plants, the increases were apparently not sufficient for protection. Treatment with HL also caused generalized damage in PSII in both types of plants. The knockdown and NT plants exhibited differences in photosynthetic parameters related to efficiency of utilization of light and CO2. The knockdown plants overexpressed other antioxidant enzymes in response to the stresses and increased the GPX activity in the chloroplast-enriched fraction. Our data suggest that a partial deficiency of chlAPX expression modulate the PSII activity and integrity, reflecting the overall photosynthesis when rice plants are subjected to acute oxidative stress. However, under normal growth conditions, the knockdown plants exhibit normal phenotype, biochemical and physiological performance. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Excited triplet state of N-(9-methylpurin-6-yl)pyridinium cation as an efficient photosensitizer in the oxidation of sulfur-containing amino acids. Laser flash and steady-state photolysis studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marciniak, B.; Hug, G.L.; Bobrowski, K.

1995-01-11

In this paper, we present and discuss the results of a detailed mechanistic study of the photosensitized oxidation of sulfur-containing amino acids by N-(9-methylpurin-6-yl)pyridinium cations in aqueous solution. The results provide data on the photoreactivity of the pyridinium salts (derived from the purine bases) in the presence of the electron donors such as sulfur-containing organic compounds and give new experimental evidence for the general mechanism of the sensitized photooxidation of thioethers proposed previously. 39 refs., 6 figs., 2 tabs.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

Oxygen optical gas sensing by reversible fluorescence quenching in photo-oxidized poly(9,9-dioctylfluorene) thin films.

PubMed

Anni, M; Rella, R

2010-02-04

We investigated the fluorescence (FL) dependence on the environment oxygen content of poly(9,9-dioctylfluorene) (PF8) thin films. We show that the PF8 interactions with oxygen are not limited to the known irreversible photo-oxidation, resulting in the formation of Keto defects, but also reversible FL quenching is observed. This effect, which is stronger for the Keto defects than for the PF8, has been exploited for the realization of a prototype oxygen sensor based on FL quenching. The sensing sensitivity of Keto defects is comparable with the state of the art organic oxygen sensors based on phosphorescence quenching.

Impact of Propene on Secondary Organic Aerosol Formation from m-Xylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Chen; Na, Kwangsam; Warren, Bethany

2007-10-15

Propene is widely used in smog chamber experiments to increase the hydroxyl radical (OH) level based on the assumption that the formation of secondary organic aerosol (SOA) from parent hydrocarbon is unaffected. A series ofm-xylene/NOx photooxidation experiments were conducted in the presence of propene in the University of California CECERT atmospheric chamber facility. The experimental data are compared with previousm-xylene/NOx photooxidation work performed in the same chamber facility in the absence of propene (Song et al. Environ. Sci. Technol. 2005, 39, 3143-3149). The result shows that, for similar initial conditions, experiments with propene have lower reaction rates of m-xylene thanmore » those without propene, which indicates that propene reduces OH in the system. Furthermore, experiments with propene showed more than 15% reduction in SOA yield compared to experiments in the absence of propene. Additional experiments ofm-xylene/NOx with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NOx photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons.« less

Nitrogen Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Tran B.; Laskin, Julia; Laskin, Alexander

2011-07-06

Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NOx conditions. Up to 80-90% of the observed products are oligomers and up to 33% are nitrogen-containing organic compounds (NOC). We observe oligomers with up to 8 monomer units in length. Tandem mass spectrometry (MSn) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C2-C5 monomer units are identified including methylglyoxal,more » hydroxyacetone, hydroxyacetic acid, glycolaldehyde, and 2-methyltetrols. The majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NOx conditions and 0.83 under the high-NOx conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.« less

Antioxidant content in two CAM bromeliad species as a response to seasonal light changes in a tropical dry deciduous forest.

PubMed

González-Salvatierra, Claudia; Luis Andrade, José; Escalante-Erosa, Fabiola; García-Sosa, Karlina; Manuel Peña-Rodríguez, Luis

2010-07-01

Plants have evolved photoprotective mechanisms to limit photodamage; one of these mechanisms involves the biosynthesis of antioxidant metabolites to neutralize reactive oxygen species generated when plants are exposed to excess light. However, it is known that exposure of plants to conditions of extreme water stress and high light intensity results in their enhanced susceptibility to over-excitation of photosystem II and to photooxidative stress. In this investigation we used the 2,2-diphenyl-1-picrylhydrazyl reduction assay to conduct a broad survey of the effect of water availability and light exposure conditions on the antioxidant activity of the leaf extracts of two bromeliad species showing crassulacean acid metabolism. One of these was an epiphyte, Tillandsia brachycaulos, and the other a terrestrial species, Bromelia karatas. Both species were found growing wild in the tropical dry deciduous forest of Dzibilchaltún National Park, México. The microenvironment of T. brachycaulos and B. karatas experiences significant diurnal and seasonal light variations as well as changes in temperature and water availability. The results obtained showed that, for both bromeliads, increases in antioxidant activity occurred during the dry season, as a consequence of water stress and higher light conditions. Additionally, in T. brachycaulos there was a clear correlation between high light intensity conditions and the content of anthocyanins which accumulated below the leaf epidermis. This result suggests that the role of these pigments is as photoprotective screens in the leaves. The red coloration below the leaf epidermis of B. karatas was not due to anthocyanins but to other unidentified pigments. 2010 Elsevier GmbH. All rights reserved.

On the in vivo photochemical rate parameters for PDT reactive oxygen species modeling

NASA Astrophysics Data System (ADS)

Kim, Michele M.; Ghogare, Ashwini A.; Greer, Alexander; Zhu, Timothy C.

2017-03-01

Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in vitro. Recent developments allow for the estimation of some of these photochemical parameters in vivo. This review will cover the currently available in vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT.

On the in-vivo photochemical rate parameters for PDT reactive oxygen species modeling

PubMed Central

Kim, Michele M.; Ghogare, Ashwini A.; Greer, Alexander; Zhu, Timothy C.

2017-01-01

Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in-vitro. Recent developments allow for the estimation of some of these photochemical parameters in-vivo. This review will cover the currently available in-vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT. PMID:28166056

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1977-01-01

Hydrogen is produced by the solar photolysis of water in a first photooxidation vessel with a transparent wall in the presence of a water soluble photooxidizable reagent and an insoluble hydrogen recombination catalyst. Simultaneously oxygen is produced in a second photoreduction reactor with a transparent wall in the presence of an insoluble photoreduction reagent catalyst. When spent, the solution from the first reactor is fed into the second reactor. A reaction occurs in the dark in which the redox reagents are regenerated, and the regenerated photooxidation reagent solution is recycled to the first reactor. The photoreduction-catalyst is a bifunctional reagent catalyst including a transition metal salt together with a hydroxyl or chlorohydroxyl decomposition catalyst of high area.

The effect of particle acidity on secondary organic aerosol formation from α-pinene photooxidation under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Han, Yuemei; Stroud, Craig A.; Liggio, John; Li, Shao-Meng

2016-11-01

Secondary organic aerosol (SOA) formation from photooxidation of α-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high- and low-NOx conditions. The SOA yield (4.2-7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6-36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of α-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early α-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0-1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of α-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after α-pinene photooxidation, suggesting a different acidity effect exists for α-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where α-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33-35 % and CxHyO2+ 16-17 %) in the total organics and the O / C ratio (0.52-0.56) of α-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39-40, 17-19, and 0.61-0.64 %), suggesting that α-pinene SOA was less oxygenated in the studied high-NOx conditions. The fraction of nitrogen-containing organic fragments (CxHyNz+ and CxHyOzNp+) in the total organics was enhanced with the increases in particle acidity under high-NOx conditions, indicating that organic nitrates may be formed heterogeneously through a mechanism catalyzed by particle acidity or that acidic conditions facilitate the partitioning of gas-phase organic nitrates into particle phase. The results of this study suggest that inorganic acidity has a significant role to play in determining various organic aerosol chemical properties such as mass yields, oxidation state, and organic nitrate content. The acidity effect being further dependent on the timescale of SOA formation is also an important parameter in the modeling of SOA.

Discovery and characterization of a photo-oxidative histidine-histidine cross-link in IgG1 antibody utilizing ¹⁸O-labeling and mass spectrometry.

PubMed

Liu, Min; Zhang, Zhongqi; Cheetham, Janet; Ren, Da; Zhou, Zhaohui Sunny

2014-05-20

A novel photo-oxidative cross-linking between two histidines (His-His) has been discovered and characterized in an IgG1 antibody via the workflow of XChem-Finder, (18)O labeling and mass spectrometry (Anal. Chem. 2013, 85, 5900-5908). Its structure was elucidated by peptide mapping with multiple proteases with various specificities (e.g., trypsin, Asp-N, and GluC combined with trypsin or Asp-N) and mass spectrometry with complementary fragmentation modes (e.g., collision-induced dissociation (CID) and electron-transfer dissociation (ETD)). Our data indicated that cross-linking occurred across two identical conserved histidine residues on two separate heavy chains in the hinge region, which is highly flexible and solvent accessible. On the basis of model studies with short peptides, it has been proposed that singlet oxygen reacts with the histidyl imidazole ring to form an endoperoxide and then converted to the 2-oxo-histidine (2-oxo-His) and His+32 intermediates, the latter is subject to a nucleophilic attack by the unmodified histidine; and finally, elimination of a water molecule leads to the final adduct with a net mass increase of 14 Da. Our findings are consistent with this mechanism. Successful discovery of cross-linked His-His again demonstrates the broad applicability and utility of our XChem-Finder approach in the discovery and elucidation of protein cross-linking, particularly without a priori knowledge of the chemical nature and site of cross-linking.

The water-water cycle is essential for chloroplast protection in the absence of stress.

PubMed

Rizhsky, Ludmila; Liang, Hongjian; Mittler, Ron

2003-10-03

Maintaining electron flow through the photosynthetic apparatus, even in the absence of a sufficient amount of NADP+ as an electron acceptor, is essential for chloroplast protection from photooxidative stress. At least two different pathways are thought to participate in this process, i.e. cyclic electron flow and the water-water cycle. Although the function of the water-water cycle was inferred from a number of biochemical and physiological studies, genetic evidence for the function of this cycle is very limited. Here we show that knockdown Arabidopsis plants with suppressed expression of the key water-water cycle enzyme, thylakoid-attached copper/zinc superoxide dismutase (KD-SOD), are suppressed in their growth and development. Chloroplast size, chlorophyll content, and photosynthetic activity were also reduced in KD-SOD plants. Microarray analysis of KD-SOD plants, grown under controlled conditions, revealed changes in transcript expression consistent with an acclimation response to light stress. Although a number of transcripts involved in the defense of plants from oxidative stress were induced in KD-SOD plants, and seedlings of KD-SOD plants were more tolerant to oxidative stress, these mechanisms were unable to compensate for the suppression of the water-water cycle in mature leaves. Thus, the localization of copper/zinc superoxide dismutase at the vicinity of photosystem I may be essential for its function. Our studies provide genetic evidence for the importance of the water-water cycle in protecting the photosynthetic apparatus of higher plants from photooxidative damage.

Production of Molecular Iodine and Tri-iodide in the Frozen Solution of Iodide: Implication for Polar Atmosphere.

PubMed

Kim, Kitae; Yabushita, Akihiro; Okumura, Masanori; Saiz-Lopez, Alfonso; Cuevas, Carlos A; Blaszczak-Boxe, Christopher S; Min, Dae Wi; Yoon, Ho-Il; Choi, Wonyong

2016-02-02

The chemistry of reactive halogens in the polar atmosphere plays important roles in ozone and mercury depletion events, oxidizing capacity, and dimethylsulfide oxidation to form cloud-condensation nuclei. Among halogen species, the sources and emission mechanisms of inorganic iodine compounds in the polar boundary layer remain unknown. Here, we demonstrate that the production of tri-iodide (I3(-)) via iodide oxidation, which is negligible in aqueous solution, is significantly accelerated in frozen solution, both in the presence and the absence of solar irradiation. Field experiments carried out in the Antarctic region (King George Island, 62°13'S, 58°47'W) also showed that the generation of tri-iodide via solar photo-oxidation was enhanced when iodide was added to various ice media. The emission of gaseous I2 from the irradiated frozen solution of iodide to the gas phase was detected by using cavity ring-down spectroscopy, which was observed both in the frozen state at 253 K and after thawing the ice at 298 K. The accelerated (photo-)oxidation of iodide and the subsequent formation of tri-iodide and I2 in ice appear to be related with the freeze concentration of iodide and dissolved O2 trapped in the ice crystal grain boundaries. We propose that an accelerated abiotic transformation of iodide to gaseous I2 in ice media provides a previously unrecognized formation pathway of active iodine species in the polar atmosphere.

Photodegradation of perfluorooctanoic acid by graphene oxide-deposited TiO2 nanotube arrays in aqueous phase.

PubMed

Park, Kyungmin; Ali, Imran; Kim, Jong-Oh

2018-07-15

Perfluorooctanoic acid (PFOA) is a persistent organic pollutant in the environment with serious health risks including endocrine-disrupting characteristics, immunotoxicity, and causing developmental defects. The photocatalytic deposition has proven to be an inexpensive, effective, and sustainable technology for the removal of PFOA in the aqueous phase. Most investigations are conducted in ultrapure water at concentrations higher than those detected in actual water systems. A few studies deal with the toxicity of treated water. In this research, the photocatalytic degradation of PFOA, including photo-oxidative and photo-reductive degradation, is reviewed comprehensively. Compared to photo-oxidation, photo-reduction is more suitable for PFOA removal since it favors defluorination of PFOA and complete mineralization. We used graphene oxide/TiO 2 nanotubes array for photocatalytic degradation of PFOA. The effects of key parameters on the photocatalytic degradation and defluorination processes of PFOA, such as initial PFOA concentration, initial pH of the solution, an initial temperature of the solution, and external bias constant potential, are addressed. We observed that at pH 3 the PFOA degradation was around 83% in 4 h, and at 75 °C almost complete PFOA degradation was observed in 2.5 h. In photoelectrocatalytic process at 2.0 V external bias 97% of PFOA was degraded in 4 h. The mechanisms of the PFOA photodegradation process are also discussed in detail. Copyright © 2018 Elsevier Ltd. All rights reserved.

Automated system for on-line determination of dimethylarsinic and inorganic arsenic by hydride generation-atomic fluorescence spectrometry.

PubMed

Chaparro, L L; Ferrer, L; Cerdà, V; Leal, L O

2012-09-01

A multisyringe flow-injection approach has been coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS) with UV photo-oxidation for dimethylarsinic (DMA), inorganic As and total As determination, depending on the pre-treatment given to the sample (extraction or digestion). The implementation of a UV lamp allows on-line photo-oxidation of DMA and the following arsenic detection, whereas a bypass leads the flow directly to the HG-AFS system, performing inorganic arsenic determination. DMA concentration is calculated by the difference of total inorganic arsenic and measurement of the photo-oxidation step. The detection limits for DMA and inorganic arsenic were 0.09 and 0.47 μg L(-1), respectively. The repeatability values accomplished were of 2.4 and 1.8%, whereas the injection frequencies were 24 and 28 injections per hour for DMA and inorganic arsenic, respectively. This method was validated by means of a solid reference material BCR-627 (muscle of tuna) with good agreement with the certified values. Satisfactory results for DMA and inorganic arsenic determination were obtained in several water matrices. The proposed method offers several advantages, such as increasing the sampling frequency, low detection limits and decreasing reagents and sample consumption, which leads to lower waste generation.

Molecular Characterization of Organosulfur Compounds in Biodiesel and Diesel Fuel Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blair, Sandra L.; MacMillan, Amanda C.; Drozd, Greg T.

Secondary organic aerosol (SOA), formed in a process of photooxidization of diesel fuel, biodiesel fuel, and 20% biodiesel fuel/80% diesel fuel mixture, are prepared under high-NOx conditions in the presence and absence of sulfur dioxide (SO2), ammonia (NH3), and relative humidity (RH). The composition of condensed-phase organic compounds in SOA is measured using several analytical techniques including aerosol mass spectrometry (AMS), high-resolution nanospray desorption electrospray ionization mass spectrometry (nano-DESI/HRMS), and ultra high resolution and mass accuracy 21T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). Results demonstrate that sulfuric acid and condensed organosulfur species formed in photooxidation experimentsmore » with SO2 are present in the SOA particles. Fewer organosulfur species are formed in the high humidity experiments, performed at RH 90%, in comparison with experiments done under dry conditions. There is a strong overlap of organosulfur species observed in this study with previous field and chamber studies of SOA. Many mass spectrometry peaks of organosulfates (R–OS(O)2OH) in field studies previously designated as biogenic or of unknown origin might have originated from anthropogenic sources, such as photooxidation of hydrocarbons present in diesel and biodiesel fuel.« less

Photochemistry of Glyoxal in Wet Aerosols: Smog Chamber Study

NASA Astrophysics Data System (ADS)

Lim, Y. B.; Kim, H.; Turpin, B. J.

2015-12-01

Aqueous chemistry is an important pathway for the formation of secondary organic aerosol (SOA). Reaction vessel studies provide evidence that in the aqueous phase photooxidation of water soluble organic compounds (e.g., glyoxal, methylglyoxal) form multifunctional organic products and oligomers. In this work, we extend this bulk-phase chemistry to the condensed-phase chemistry that occurs in/on aerosols by conducting smog chamber experiments — photooxidation of ammonium sulfate and sulfuric acid aerosols containing glyoxal and hydrogen peroxide in the presence of NOx under dry/humid conditions. Particles were analyzed using ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). In the irradiated chamber, photooxidation products of glyoxal as seen in reaction vessel experiments (e.g., oxalic acids and tartaric acids) were also formed in both ammonium sulfate aerosols and sulfuric acid aerosols at humid and even dry conditions. However, the major products were organosulfurs (CHOS), organonitrogens (CHON), and nitrooxy-organosulfates (CHONS), which were also dominantly formed in the dark chamber. These products were formed via non-radical reactions, which depend on acidity and humidity. However, the real-time profiles in the dark chamber and the irradiated chamber were very different, suggesting photochemistry substantially affects non-radical formation in the condensed phase.

Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

PubMed

Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

2013-01-01

The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

Heterogeneous photo-oxidation of pesticides and its implication to their environmental fate

NASA Astrophysics Data System (ADS)

Dubowski, Y.

2014-12-01

The environmental fate and impact of pesticides strongly depend on their post application degradation processes. While most existing knowledge on pesticides degradation refers to processes within bulk soil and water, applied pesticides may remain on treated surfaces (and on airborn particles) for long duration, exposed to atmospheric oxidants and solar radiation. The resulting photo-oxidation processes may have significant effect on their fate, especially in semiarid regions where pesticide applications take place during the long dry season and targeted irrigation is common. Here we present our studies on heterogeneous photo-oxidation of few commonly used pesticides (e.g., cypermethrin, methyl parathion, and chlorpyrifos), using novel laboratory setups enabling simultaneous monitoring of both phases. Experiments focused on kinetics, quantum yields, and identification of gaseous and condensed products. In addition, the reactivity of the selected pesticides was investigated as a function of their matrix (analytical vs. commercial formula), their phase (thin film vs. airborne aerosols), and the substrate they are sorbed on (leaf, soil, and glass). Complimentarily to these laboratory studies, field measurements of selected pesticides concentrations in few streams in northern Israel during the first rain events were also conducted and showed the important role of surface processes on these pesticides fate and transport in semi-arid climate.

Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

PubMed

Ward, Collin P; Cory, Rose M

2016-04-05

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

Mutagenic atmospheres resulting from the photooxidation of aromatic hydrocarbon and NOx mixtures

NASA Astrophysics Data System (ADS)

Riedel, Theran P.; DeMarini, David M.; Zavala, Jose; Warren, Sarah H.; Corse, Eric W.; Offenberg, John H.; Kleindienst, Tadeusz E.; Lewandowski, Michael

2018-04-01

Although many volatile organic compounds (VOCs) are regulated to limit air pollution and the consequent health effects, the photooxidation products generally are not. Thus, we examined the mutagenicity in Salmonella TA100 of photochemical atmospheres generated in a steady-state atmospheric simulation chamber by irradiating mixtures of single aromatic VOCs, NOx, and ammonium sulfate seed aerosol in air. The 10 VOCs examined were benzene; toluene; ethylbenzene; o-, m-, and p-xylene; 1,2,4- and 1,3,5-trimethylbenzene; m-cresol; and naphthalene. Salmonella were exposed at the air-agar interface to the generated atmospheres for 1, 2, 4, 8, or 16 h. Dark-control exposures produced non-mutagenic atmospheres, illustrating that the gas-phase precursor VOCs were not mutagenic at the concentrations tested. Under irradiation, all but m-cresol and naphthalene produced mutagenic atmospheres, with potencies ranging from 2.0 (p-xylene) to 11.4 (ethylbenzene) revertants m3 mgC-1 h-1. The mutagenicity was due exclusively to direct-acting late-generation products of the photooxidation reactions. Gas-phase chemical analysis showed that a number of oxidized organic chemical species enhanced during the irradiated exposure experiments correlated (r ≥ 0.81) with the mutagenic potencies of the atmospheres. Molecular formulas assigned to these species indicated that they likely contained peroxy acid, aldehyde, alcohol, and other functionalities.

Assessing the role of solar radiation in heating, photosynthesis, and photo-oxidation in upper Arctic Ocean waters via autonomous buoys

NASA Astrophysics Data System (ADS)

Hill, V. J.; Steele, M.; Light, B.

2016-02-01

As part of the Arctic Observing Network, a new ice-tethered buoy has been developed for monitoring the role of sunlight in regulating ocean temperature, phytoplankton growth, and carbon cycling. A 20 or 50 m string (depending on local bathymetry) supports sensors both within and below the ice for the hourly measurement of downwelling irradiance, temperature, Chlorophyll a, light backscattering, and dissolved organic material (DOM). Two buoys were deployed in March 2014 and two in March 2015. Because the buoys are engineered to survive melting out of first year ice, they have successfully provided complete seasonal records of water column warming, phytoplankton abundance and photo-oxidation patterns in the Pacific Arctic Region. The data collected will be used to determine whether reduced ice extent and thinner ice are driving increases in under ice warming, accelerating bottom ice ablation, increasing available photosynthetic radiation to support large under ice blooms, and to quantify photo-oxidation of the DOM pool. Observations so far have revealed strong under ice daily warming as high as ±0.5 °C driven by local solar radiation. Water column absorption was dominated by colored dissolved organic material which served to trap solar radiation in the upper water column. Chlorophyll concentrations observed in June and July indicated high phytoplankton abundance beneath the ice. Light intensity at this time was not sufficient to support growth rates high enough to produce the 8 to 10 mg m-3 of chlorophyll observed. We hypothesize that phytoplankton were advected under the ice from the ice edge. However, once there phytoplankton were able to sustain low growth rates leading to nutrient limitation before open water status was reached. Strong daily cycles of photo-oxidation have also been observed in the late summer that indicate the fast cycling of highly labile DOM in the open waters of the Pacific Arctic Region.

Plasma lipoproteins as mediators of the oxidative stress induced by UV light in human skin: a review of biochemical and biophysical studies on mechanisms of apolipoprotein alteration, lipid peroxidation, and associated skin cell responses.

PubMed

Filipe, Paulo; Morlière, Patrice; Silva, João N; Mazière, Jean-Claude; Patterson, Larry K; Freitas, João P; Santus, R

2013-01-01

There are numerous studies concerning the effect of UVB light on skin cells but fewer on other skin components such as the interstitial fluid. This review highlights high-density lipoprotein (HDL) and low-density lipoprotein (LDL) as important targets of UVB in interstitial fluid. Tryptophan residues are the sole apolipoprotein residues absorbing solar UVB. The UVB-induced one-electron oxidation of Trp produces (•)Trp and (•)O2 (-) radicals which trigger lipid peroxidation. Immunoblots from buffered solutions or suction blister fluid reveal that propagation of photooxidative damage to other residues such as Tyr or disulfide bonds produces intra- and intermolecular bonds in apolipoproteins A-I, A-II, and B100. Partial repair of phenoxyl tyrosyl radicals (TyrO(•)) by α -tocopherol is observed with LDL and HDL on millisecond or second time scales, whereas limited repair of α -tocopherol by carotenoids occurs in only HDL. More effective repair of Tyr and α -tocopherol is observed with the flavonoid, quercetin, bound to serum albumin, but quercetin is less potent than new synthetic polyphenols in inhibiting LDL lipid peroxidation or restoring α -tocopherol. The systemic consequences of HDL and LDL oxidation and the activation and/or inhibition of signalling pathways by oxidized LDL and their ability to enhance transcription factor DNA binding activity are also reviewed.

Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

NASA Astrophysics Data System (ADS)

Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

2013-12-01

Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self-cyclization also affects NOx-dependence of SOA formation. Comparison of SOA formation yield and composition between two aromatics implies aldehyde/ketone chemistry from ring-opening route and chemistry for phenolic route play important roles in governing SOA formation and that ring-opening aldehydes and phenolic nitrates are produced to a greater extent in the toluene system, leading to higher SOA yields for toluene than for m-xylene.

Photo-oxidation of Polymers Synthesized by Plasma and Initiated CVD

DOE PAGES

Baxamusa, Salmaan H.; Suresh, Aravind; Ehrmann, Paul; ...

2015-11-09

Plasma polymers are often limited by their susceptibility to spontaneous and photo-oxidation. We show that the unusual photoluminescence (PL) behavior of a plasma polymer of trans-2-butene is correlated with its photoluminescence strength. These photo-processes occur under blue light illumination (λ=405 nm), distinguishing them from traditional ultraviolet degradation of polymers. These photo-active defects are likely formed during the plasma deposition process and we show that a polymer synthesized using initiated (i)CVD, non-plasma method, has 1000× lower PL signal and enhanced photo-stability. In conclusion, non-plasma methods such as iCVD may therefore be a route to overcoming material aging issues that limit themore » adoption of plasma polymers.« less

Laser-based trace gas detection of ethane as a result of photo-oxidative damage in chilled cucumber leaves (invited)

NASA Astrophysics Data System (ADS)

Santosa, I. E.; Laarhoven, L. J. J.; Harbinson, J.; Driscoll, S.; Harren, F. J. M.

2003-01-01

At low temperatures, high light intensity induces strong photooxidative lipid peroxidation in chilling sensitive cucumber leaves. A sensitive laser-based photoacoustic detector was employed to monitor on-line the evolution of ethane, one of the end products of lipid peroxidation. The Δv=2 CO laser operated in the 2.62-4.06 μm infrared wavelength region with a maximum intracavity power of 11 W. In combination with an intracavity placed photoacoustic cell the laser was able to detect ethane down to 0.5 part per billion. Cucumber leaf disks chilled in the light produce ethane; the rate of ethane production depends on the applied temperature, light intensity, and period of chilling.

A Systematic Evaluation of the Extent of Photochemical Processing in Different Types of Secondary Organic Aerosols in the Aqueous Phase

NASA Astrophysics Data System (ADS)

Romonosky, D.; Lee, H.; Epstein, S. A.; Nizkorodov, S.; Laskin, J.; Laskin, A.

2013-12-01

A significant fraction of atmospheric organic compounds are predominantly found in condensed phases, such as organic phase in aerosol particles or aqueous phase in cloud droplets. The oxidation of VOCs followed by the condensation of products into particles was thought to be the main mechanism of organic aerosol (OA) formation. However, in the last several years, scientists have realized that a large fraction, if not the majority of organic particles, is produced through cloud and fog photochemical processes. Many of these organic compounds are photolabile, and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days). We previously reported that compounds in secondary organic aerosol (SOA) from ozonolysis of d-limonene efficiently photodegrade in both organic (Walser et al., 2007) and aqueous phases (Bateman et al., 2011). Significant photolysis was also observed in an aqueous extract of SOA from high-NOx photooxidation of isoprene (Nguyen et al., 2012). More recent experiments studying the response to irradiation of complex aqueous mixtures (as opposed to solutions of isolated compounds) found surprising resilience to photodegradation in aqueous extracts of SOA prepared by photooxidation of alpha-pinene (Romonosky et al., unpublished). We present a systematic investigation of the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic precursors. Chamber- or flowtube-generated SOA is collected on an inert substrate, extracted in a methanol/water solution (70:30), photolyzed in the aqueous solution, and the extent of change in the molecular level composition of the material is assessed with high-resolution mass spectrometry (HR-MS). The outcome of this study will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets. Bateman et al. Photolytic processing of secondary organic aerosols dissolved in cloud droplets. Phys. Chem. Chem. Phys. 2011, 13, 12199. Nguyen et al. Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol. Phys. Chem. Chem. Phys. 2012, 14, 9702. Walser et al. Photochemical aging of secondary organic aerosol particles generated from the oxidation of d-limonene. J. Phys. Chem. A 2007, 111, 1907.

Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

NASA Astrophysics Data System (ADS)

Beardsley, Ross L.; Jang, Myoseon

2016-05-01

The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and simulated YSOA increase and are found to be more sensitive to [H+] and LWC. For atmospherically relevant conditions, YSOA is found to be more than 150 % higher in partially titrated acidic seeds (NH4HSO4) than in effloresced inorganics or in isoprene only.

Studies of Physicochemical Processes in Atmospheric Particles and Acid Deposition.

NASA Astrophysics Data System (ADS)

Pandis, Spyros N.

A comprehensive chemical mechanism for aqueous -phase atmospheric chemistry was developed and its detailed sensitivity analysis was performed. The main aqueous-phase reaction pathways for the system are the oxidation of S(IV) to S(VI) by H_2O_2 , OH, O_2 (catalysed by Fe ^{3+} and Mn^ {2+}), O_3 and HSO_sp{5}{-}. The gas-phase concentrations of SO_2, H_2O_2, HO _2, OH, O_3 HCHO, NH_3, HNO_3 and HCl and the liquid water content of the cloud are of primary importance. The Lagrangian model predictions for temperature profile, fog development, liquid water content, gas-phase concentrations of SO_2 , HNO_3, and NH_3 , pH, aqueous-phase concentrations of SO _sp{4}{2-}, NH _sp{4}{+} and NO _sp{3}{-}, and finally deposition rates of the above ions match well the observed values. A third model was developed to study the distribution of acidity and solute concentration among the various droplet sizes in a fog or a cloud. Significant solute concentration differences can occur in aqueous droplets inside a fog or a cloud. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations, but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium as well as in the total aerosol mass concentration. The sulfate producd during fog episodes favors the aerosol particles that have access to most of the fog liquid water. Aerosol scavenging efficiencies of around 80% were calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition. Isoprene and beta-pinene, at concentration levels ranging from a few ppb to a few ppm were reacted photochemically with NO_ {x} in the Caltech outdoor smog chamber facility. Aerosol formation from the isoprene photooxidation was found to be negligible even under extreme ambient conditions due to the relatively high vapor pressure of its condensable products. Aerosol carbon yield from the beta -pinene photooxidation is as high as 8% and depends strongly on the initial HC/NO_{x} ratio. Monoterpene photooxidation can be a significant source of secondary aerosol in rural environments and in urban areas with extended natural vegetation. (Abstract shortened with permission of author.).

Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

NASA Astrophysics Data System (ADS)

Zhao, Defeng; Schmitt, Sebastian H.; Wang, Mingjin; Acir, Ismail-Hakki; Tillmann, Ralf; Tan, Zhaofeng; Novelli, Anna; Fuchs, Hendrik; Pullinen, Iida; Wegener, Robert; Rohrer, Franz; Wildt, Jürgen; Kiendler-Scharr, Astrid; Wahner, Andreas; Mentel, Thomas F.

2018-02-01

Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: < 1to 20 ppb, SO2: < 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57-77 %), even in low-NOx conditions (< ˜ 1 ppb). Organic nitrate contributed 7-26 % of total organics assuming a molecular weight of 200 g mol-1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H / C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.

Kinetics of photoinduced electron transfer reactions of ruthenium(II) complexes and phenols, tyrosine, N-acetyl-tyrosine and tryptophan in aqueous solutions measured with modulated fluorescence spectroscopy.

PubMed

Nguyen, Truong X; Landgraf, Stephan; Grampp, Günter

2017-01-01

Photooxidation kinetics of phenol, 1-naphthol, 2-naphthol, tyrosine (TyrOH) and N-acetyl-tyrosine (AcTyrOH), tryptophan (TrpH) by ruthenium(II) polypyridyl complexes: [Ru(bpy) 3 ]Cl 2 (1), [Ru(phen) 3 ]Cl 2 (2), [Ru(bpy)(phen)(bpg)]Cl 2 (3), and [Ru(dpq) 2 (bxbg)]Cl 2 (4) where bpy is 2,2'-bipyridine, phen - 1,10-phenanthroline, bpg - bipyridine-glycoluril, dpq - dipyrido[3,2-d:2',3'-f]quinoxaline, and bxbg - bis(o-xylene)bipyridine-glycoluril are investigated. Rate constants have been measured by steady-state luminescence and phase-modulation fluorometry in aqueous solutions at different pH's. The rates for the oxidation of the phenols and phenolic aromatic amino acids spreads over a wide range from 4.2×10 6 to 6.8×10 9 M -1 s -1 , depending on pH and the nature of solutes. At pH>pK a of the quenchers, the presence of reactive species (PhO - ) in the alkaline solutions is accounted for the rapid ET rates. In the pH range between 4 and 10 (pH

Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa

PubMed Central

Pham, Nhi-Thi; Kim, Jin-Gil; Jung, Sunyo

2015-01-01

We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF) or methyl viologen (MV). Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD) and catalase (CAT) as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX) activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2) is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS) production under photooxidative stress caused by OF and MV. PMID:26197316

Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa.

PubMed

Pham, Nhi-Thi; Kim, Jin-Gil; Jung, Sunyo

2015-07-21

We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF) or methyl viologen (MV). Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD) and catalase (CAT) as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX) activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2) is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS) production under photooxidative stress caused by OF and MV.

Biosynthetic porphyrins and the origin of photosynthesis

NASA Technical Reports Server (NTRS)

Mauzerall, D.; Ley, A.; Mercer-Smith, J. A.

1986-01-01

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

Photooxidation of Amplex Red to resorufin: implications of exposing the Amplex Red assay to light

PubMed Central

Zhao, Baozhong; Summers, Fiona A.; Mason, Ronald P.

2012-01-01

The Amplex Red assay, a fluorescent assay for the detection of H2O2, relies on the reaction of H2O2 and colorless, nonfluorescent Amplex Red with a 1:1 stoichiometry to form colored, fluorescent resorufin, catalyzed by horseradish peroxidase (HRP). We have found that resorufin is artifactually formed when Amplex Red is exposed to light. In the absence of H2O2 and HRP, the absorption and fluorescence spectra of Amplex Red changed during exposure to ambient room light or instrumental excitation light, clearly indicating that the fluorescent product resorufin had formed. This photochemistry was initiated by trace amounts of resorufin that are present in Amplex Red stock solutions. ESR spin-trapping studies demonstrated that superoxide radical was an intermediate in this process. Oxygen consumption measurements further confirmed that superoxide and H2O2 were artifactually produced by the photooxidation of Amplex Red. The artifactual formation of resorufin was also significantly increased by the presence of superoxide dismutase or HRP. This photooxidation process will result in a less sensitive assay for H2O2 under ambient light exposure and potentially invalid measurements under high energy exposure such as UVA irradiation. In general, precautions should be taken to minimize exposure to light during measurement of oxidative stress with Amplex Red. PMID:22765927

Photooxidation of Amplex Red to resorufin: implications of exposing the Amplex Red assay to light.

PubMed

Zhao, Baozhong; Summers, Fiona A; Mason, Ronald P

2012-09-01

The Amplex Red assay, a fluorescent assay for the detection of H(2)O(2), relies on the reaction of H(2)O(2) and colorless, nonfluorescent Amplex Red with a 1:1 stoichiometry to form colored, fluorescent resorufin, catalyzed by horseradish peroxidase (HRP). We have found that resorufin is artifactually formed when Amplex Red is exposed to light. In the absence of H(2)O(2) and HRP, the absorption and fluorescence spectra of Amplex Red changed during exposure to ambient room light or instrumental excitation light, clearly indicating that the fluorescent product resorufin had formed. This photochemistry was initiated by trace amounts of resorufin that are present in Amplex Red stock solutions. ESR spin-trapping studies demonstrated that superoxide radical was an intermediate in this process. Oxygen consumption measurements further confirmed that superoxide and H(2)O(2) were artifactually produced by the photooxidation of Amplex Red. The artifactual formation of resorufin was also significantly increased by the presence of superoxide dismutase or HRP. This photooxidation process will result in a less sensitive assay for H(2)O(2) under ambient light exposure and potentially invalid measurements under high energy exposure such as UVA irradiation. In general, precautions should be taken to minimize exposure to light during measurement of oxidative stress with Amplex Red. Published by Elsevier Inc.

Photophysical and photochemical effects of UV and VUV photo-oxidation and photolysis on PET and PEN

NASA Astrophysics Data System (ADS)

Morgan, Andrew

Polyethylene Terephthalate (PET) is a widely used polymer in the bottling, packaging, and clothing industry. In recent years an increasing global demand for PET has taken place due to the Solar Disinfection (SODIS) process. SODIS is a method of sterilizing fresh water into drinkable water. The PET bottles are used in the process to contain the water during solar irradiation due to its highly transparent optical property. Alongside PET, polyethylene 2,6-napthalate (PEN) is used in bottling and flexible electronic applications. The surface of PEN would need to be modified to control the hydrophilicity and the interaction it exudes as a substrate. The UV light absorption properties of PET and PEN are of great importance for many applications, and thus needs to be studied along with its photochemical resistance. The optical and chemical nature of PET was studied as it was treated by UV photo-oxidation, photo-ozonation, and photolysis under atmospheric pressure. Another investigation was also used to study PEN and PET as they are treated by vacuum UV (VUV) photo-oxidation, VUV photolysis, and remote oxygen reactions. The extent of the photoreactions' effect into the depth of the polymers is examined as treatment conditions are changed. The different experimental methods established the rate of several competing photoreactions on PET and PEN during irradiance, and their effect on the optical quality of the polymers.

Photodynamic evaluation of tetracarboxy-phthalocyanines in model systems.

PubMed

Alonso, Lais; Sampaio, Renato N; Souza, Thalita F M; Silva, Rodrigo C; Neto, Newton M Barbosa; Ribeiro, Anderson O; Alonso, Antonio; Gonçalves, Pablo J

2016-08-01

The present work reports the synthesis, photophysical and photochemical characterization and photodynamic evaluation of zinc, aluminum and metal free-base tetracarboxy-phthalocyanines (ZnPc, AlPc and FbPc, respectively). To evaluate the possible application of phthalocyanines as a potential photosensitizer the photophysical and photochemical characterization were performed using aqueous (phosphate-buffered solution, PBS) and organic (dimethyl sulfoxide, DMSO) solvents. The relative lipophilicity of the compounds was estimated by the octanol-water partition coefficient and the photodynamic activity evaluated through the photooxidation of a protein and photohemolysis. The photooxidation rate constants (k) were obtained and the hemolytic potential was evaluated by the maximum percentage of hemolysis achieved (Hmax) and the time (t50) to reach 50% of the Hmax. Although these phthalocyanines are all hydrophilic and possess very low affinity for membranes (log PO/W=-2.0), they led to significant photooxidation of bovine serum albumin (BSA) and photohemolysis. Our results show that ZnPc was the most efficient photosensitizer, followed by AlPc and FbPc; this order is the same as the order of the triplet and singlet oxygen quantum yields (ZnPc>AlPc>FbPc). Furthermore, together, the triplet, fluorescence and singlet oxygen quantum yields of zinc tetracarboxy-phthalocyanines suggest their potential for use in theranostic applications, which simultaneously combines photodiagnosis and phototherapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Secondary organic aerosol and ozone formation from photo-oxidation of unburned diesel fuel in a surrogate atmospheric environment

NASA Astrophysics Data System (ADS)

Li, Weihua; Cocker, David R.

2018-07-01

Diesel fuel is a complex mixture of intermediate volatility organic compounds (IVOCs). Previous studies focused on secondary organic aerosol (SOA) and ozone formation from photo-oxidation of organic vapor from diesel exhaust and their components such as aromatics and heavy alkanes. However, there are few studies on atmospheric behavior of unburnt diesel. Therefore, in this study, ten unburnt #2 commercial diesel samples and one FACE9A research diesel fuel were photo-oxidized in the University of California Riverside, College of Engineering-Center for Environmental Research & Technology dual environmental chambers to investigate their SOA and ozone production potential. Photochemical aging rapidly produced significant SOA (yield ∼20.3-37.7%) in the presence of a surrogate reactive organic gas (ROG) mixture used to mimic urban atmospheric reactivity. SOA yields were consistent with n-Heptadecane yields under similar conditions. Doubling NOx concentrations within relevant urban concentration levels enhanced SOA formation by 33% and ozone formation by 48%. SOA formation in this study was approximately fourteen times higher than previously reported for very high NOx conditions. An SOA experiment designed to mimic the previous work achieved similar yields to the earlier work. SOA formed under urban relevant NOx concentrations were consistent with semi-volatile-oxygenated organic aerosol (SV-OOA) and underwent little further chemical processing once produced.

EPR spin trapping evidence of radical intermediates in the photo-reduction of bicarbonate/CO2 in TiO2 aqueous suspensions.

PubMed

Molinari, Alessandra; Samiolo, Luca; Amadelli, Rossano

2015-05-01

Using the EPR spin trapping technique, we prove that simultaneous reactions take place in illuminated suspensions of TiO2 in aqueous carbonate solutions (pH ≈ 7). The adsorbed HCO3(-) is reduced to formate as directly made evident by the detection of formate radicals (˙CO2(-)). In addition, the amount of OH˙ radicals from the photo-oxidation of water shows a linear dependence on the concentration of bicarbonate, indicating that electron scavenging by HCO3(-) increases the lifetime of holes. In a weakly alkaline medium, photo-oxidation of HCO3(-)/CO3(2-) to ˙CO3(-) interferes with the oxidation of water. A comparative analysis of different TiO2 samples shows that formation of ˙CO2(-) is influenced by factors related to the nature of the surface, once expected surface area effects are accounted for. Modification of the TiO2 surface with noble metal nanoparticles does not have unequivocal benefits: the overall activity improves with Pd and Rh but not with Ru, which favours HCO3(-) photo-oxidation even at pH = 7. In general, identification of radical intermediates of oxidation and reduction reactions can provide useful mechanistic information that may be used in the development of photocatalytic systems for the reduction of CO2 also stored in the form of carbonates.

Protective effects of resveratrol and its analogs on age-related macular degeneration in vitro.

PubMed

Kang, Jung-Hwan; Choung, Se-Young

2016-12-01

Damage of retinal pigment epithelial (RPE) cells by A2E may be critical for age-related macular degeneration (AMD) management. Accumulation and photooxidation of A2E are known to be one of the critical causes in AMD. Here, we evaluated the protective effect of resveratrol (RES), piceatannol (PIC) and RES glycones on blue-light-induced RPE cell death caused by A2E photooxidation. A2E treatment followed by blue light exposure caused significant damages on human RPE cells (ARPE-19). But the damages were attenuated by post- and pre-treatment of RES and PIC in our in vitro models. The results of cell free system and FAB-MS analysis clearly showed that the reduction of A2E by blue light exposure was significantly rescued, and that oxidized forms of A2E were significantly reduced by RES or PIC treatment. Besides, RES or PIC inhibited the intracellular accumulation of A2E. Not only RES and PIC but RES glycones showed protection of ARPE-19 cells against A2E and blue-light-induced photo-damage. These findings demonstrate that RES and its analogs may have protective effects against A2E and blue-light-induced ARPE-19 cell death through regulation of A2E accumulation as well as photooxidation of A2E. Thus RES and its analogs may be beneficial for AMD treatment.

Singlet-triplet fission of carotenoid excitation in light-harvesting LH2 complexes of purple phototrophic bacteria.

PubMed

Klenina, I B; Makhneva, Z K; Moskalenko, A A; Gudkov, N D; Bolshakov, M A; Pavlova, E A; Proskuryakov, I I

2014-03-01

The current generally accepted structure of light-harvesting LH2 complexes from purple phototrophic bacteria conflicts with the observation of singlet-triplet carotenoid excitation fission in these complexes. In LH2 complexes from the purple bacterium Allochromatium minutissimum, a drop in the efficiency of carotenoid triplet generation is demonstrated, which correlates with the extent of selective photooxidation of bacteriochlorophylls absorbing at ~850 nm. We conclude that singlet-triplet fission of carotenoid excitation proceeds with participation of these excitonically coupled bacteriochlorophylls. In the framework of the proposed mechanism, the contradiction between LH2 structure and photophysical properties of carotenoids is eliminated. The possibility of singlet-triplet excitation fission involving a third mediator molecule was not considered earlier.

Dynamic light absorption of biomass burning organic carbon photochemically aged under natural sunlight

NASA Astrophysics Data System (ADS)

Zhong, M.; Jang, M.

2013-08-01

Wood burning aerosol produced under smoldering conditions was photochemically aged with different relative humidity (RH) and NOx conditions using a 104 m3 dual outdoor chamber under natural sunlight. Light absorption of organic carbon (OC) was measured over the course of photooxidation using a UV-visible spectrometer connected to an integrating sphere. At high RH, the color decayed rapidly. NOx slightly prolonged the color of wood smoke, suggesting that NOx promotes the formation of chromophores via secondary processes. Overall, the mass absorption cross-section (integrated between 280 nm and 600 nm) of OC increased by 11-54% (except high RH) in the morning and then gradually decreased by 19-68% in the afternoon. This dynamic change in light absorption of wood burning OC can be explained by two mechanisms: chromophore formation and sunlight bleaching. To investigate the effect of chemical transformation on light absorption, wood smoke particles were characterized using various spectrometers. The intensity of fluorescence, which is mainly related to polycyclic aromatic hydrocarbons (PAHs), rapidly decreased with time indicating the potential bleaching of PAHs. A decline of levoglucosan concentrations evinced the change of POA with time. The aerosol water content measured by Fourier transform infrared spectroscopy showed that wood burning aerosol became less hygroscopic as photooxidation proceeded. A similar trend in light absorption changes has been observed in ambient smoke aerosol originating from the 2012 County Line Wildfire in Florida. We conclude that the biomass burning OC becomes less light absorbing after 8-9 h sunlight exposure compared to fresh wood burning OC.

Dynamic light absorption of biomass-burning organic carbon photochemically aged under natural sunlight

NASA Astrophysics Data System (ADS)

Zhong, M.; Jang, M.

2014-02-01

Wood-burning aerosol produced under smoldering conditions was photochemically aged with different relative humidity (RH) and NOx conditions using a 104 m3 dual outdoor chamber under natural sunlight. Light absorption of organic carbon (OC) was measured over the course of photooxidation using a UV-visible spectrometer connected to an integrating sphere. At high RH, the color decayed rapidly. NOx slightly prolonged the color of wood smoke, suggesting that NOx promotes the formation of chromophores via secondary processes. Overall, the mass absorption cross section (integrated between 280 and 600 nm) of OC increased by 11-54% (except high RH) in the morning and then gradually decreased by 19-68% in the afternoon. This dynamic change in light absorption of wood-burning OC can be explained by two mechanisms: chromophore formation and sunlight bleaching. To investigate the effect of chemical transformation on light absorption, wood smoke particles were characterized using various spectrometers. The intensity of fluorescence, which is mainly related to polycyclic aromatic hydrocarbons (PAHs), rapidly decreased with time, indicating the potential bleaching of PAHs. A decline of levoglucosan concentrations evinced the change of primary organic aerosol with time. The aerosol water content measured by Fourier transform infrared spectroscopy showed that wood-burning aerosol became less hygroscopic as photooxidation proceeded. A similar trend in light absorption changes has been observed in ambient smoke aerosol originating from the 2012 County Line wildfire in Florida. We conclude that the biomass-burning OC becomes less light absorbing after 8-9 h sunlight exposure compared to fresh wood-burning OC.

Photocatalyst of Perovskite CaTiO3 Nanopowder Synthesized from CaO derived from Snail Shell in Comparison with The Use of CaO and CaCO3

NASA Astrophysics Data System (ADS)

Fatimah, I.; Rahmadianti, Y.; Pudiasari, R. A.

2018-04-01

Calcium titanate belongs to the important group of compounds with a perovskite structure having high dielectric loss for various applications including photocatalysis mechanism. Refer to the principles of green chemistry, in this work preparation of CaTiO3 was conducted by using CaO derived from snail shell. Aim of this research are to study the physicochemical character of perovskite derived from snail shell and its comparison with CaO and CaCO3 as Ca sources. Material preparation was performed by solid reaction of Ca sources with TiO2 under comparison with CaO and CaCO3 precursors. Mixture of Ca sources with TiO2 in certain proportion were ground and calcined at the temperature of 200 °C for 2 hs. Materials were characterized by using X-ray diffractometer (XRD), Fourier Transform-Infra Red (FTIR) and the photocatalytic activity was tested by using methylene blue photooxidation. Perovskite synthesized using CaO derived from snail shell exhibits the similar XRD pattern with that were prepared by using CaO and CaCO3. From the photooxidation activity test, it is proven that CaTiO3 shows similar photocatalytic activity correspond to that were prepared by CaO and CaCO3. Utilazation of shell as agricultural waste of the synthesis of CaTiO3 perovskite is the novelty of this work. Furthermore, the study on material structure and photoactivity is the main focuses for the application in industry and environment.

Temperature and Plant Adaptation. I. Interaction of Temperature and Light in the Synthesis of Chlorophyll in Corn 1

PubMed Central

McWilliam, J. R.; Naylor, A. W.

1967-01-01

The effect of temperature and light intensity have been studied in relation to the greening of etiolated corn (Zea mays cv. Pioneer 309-B) seedlings. Chlorophyll accumulation is rapid at high temperature (28°) under all conditions of light intensity. At low temperature (16°), and particularly in combination with high light intensity (3000-4500 ft-c), the accumulation of both chlorophyll and carotene is inhibited. Low pigment content at 16° is not directly due to a block in the pigment synthesizing mechanism, but rather to the photodestruction of chlorophyll prior to its stabilization in the membrane structure of the chloroplast lamellae. The parallel reduction in carotene content at high light intensity is probably a contributing factor, because of its role in protecting chlorophyll from photodestruction. The greater severity of photo-oxidation of chlorophyll at low temperature in corn when compared with wheat, appears to be due to a slower rate of protochlorophyllide synthesis and subsequent esterification. Thus in corn at 16° there is a prolongation of the photosensitive stage during chlorophyll synthesis. Photo-oxidation at 16° has also been shown to be a function of the incident light energy, with the photosynthetic pigments acting as receptors for their own destruction. In comparison with the behavior of corn, wheat seedlings green rapidly at high light intensity at both 16° and 28°. This contrasting temperature response with respect to chlorophyll synthesis may underlie a fundamental difference in adaptation of these 2 species to growth in the temperate zones of the world. PMID:16656709

Improvements in serial femtosecond crystallography of photosystem II by optimizing crystal uniformity using microseeding procedures

DOE PAGES

Ibrahim, Mohamed; Chatterjee, Ruchira; Hellmich, Julia; ...

2015-07-01

In photosynthesis, photosystem II (PSII) is the multi-subunit membrane protein complex that catalyzes photo-oxidation of water into dioxygen through the oxygen evolving complex (OEC). To understand the water oxidation reaction, it is important to get structural information about the transient and intermediate states of the OEC in the dimeric PSII core complex (dPSIIcc). In recent times, femtosecond X-ray pulses from the free electron laser (XFEL) are being used to obtain X-ray diffraction (XRD) data of dPSIIcc microcrystals at room temperature that are free of radiation damage. In our experiments at the XFEL, we used an electrospun liquid microjet setup thatmore » requires microcrystals less than 40 μm in size. In this study, we explored various microseeding techniques to get a high yield of monodisperse uniform-sized microcrystals. Monodisperse microcrystals of dPSIIcc of uniform size were a key to improve the stability of the jet and the quality of XRD data obtained at the XFEL. This was evident by an improvement of the quality of the datasets obtained, from 6.5 Å, using crystals grown without the micro seeding approach, to 4.5 Å using crystals generated with the new method.« less

Confirming Pseudomonas putida as a reliable bioassay for demonstrating biocompatibility enhancement by solar photo-oxidative processes of a biorecalcitrant effluent.

PubMed

García-Ripoll, A; Amat, A M; Arques, A; Vicente, R; Ballesteros Martín, M M; Pérez, J A Sánchez; Oller, I; Malato, S

2009-03-15

Experiments based on Vibrio fischeri, activated sludge and Pseudomonas putida have been employed to check variation in the biocompatibility of an aqueous solution of a commercial pesticide, along solar photo-oxidative process (TiO(2) and Fenton reagent). Activated sludge-based experiments have demonstrated a complete detoxification of the solution, although important toxicity is still detected according to the more sensitive V. fischeri assays. In parallel, the biodegradability of organic matter is strongly enhanced, with BOD(5)/COD ratio above 0.8. Bioassays run with P. putida have given similar trends, remarking the convenience of using P. putida culture as a reliable and reproducible method for assessing both toxicity and biodegradability, as a substitute to other more time consuming methods.

High throughput photo-oxidations in a packed bed reactor system.

PubMed

Kong, Caleb J; Fisher, Daniel; Desai, Bimbisar K; Yang, Yuan; Ahmad, Saeed; Belecki, Katherine; Gupton, B Frank

2017-12-01

The efficiency gains produced by continuous-flow systems in conducting photochemical transformations have been extensively demonstrated. Recently, these systems have been used in developing safe and efficient methods for photo-oxidations using singlet oxygen generated by photosensitizers. Much of the previous work has focused on the use of homogeneous photocatalysts. The development of a unique, packed-bed photoreactor system using immobilized rose bengal expands these capabilities as this robust photocatalyst allows access to and elaboration from these highly useful building blocks without the need for further purification. With this platform we were able to demonstrate a wide scope of singlet oxygen ene, [4+2] cycloadditions and heteroatom oxidations. Furthermore, we applied this method as a strategic element in the synthesis of the high-volume antimalarial artemisinin. Copyright © 2017. Published by Elsevier Ltd.

In Situ Hydrocarbon Degradation by Indigenous Nearshore Bacterial Populations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherrier, J.

Potential episodic hydrocarbon inputs associated with oil mining and transportation together with chronic introduction of hydrocarbons via urban runoff into the relatively pristine coastal Florida waters poses a significant threat to Florida's fragile marine environment. It is therefore important to understand the extent to which indigenous bacterial populations are able to degrade hydrocarbon compounds and also determine factors that could potentially control and promote the rate at which these compounds are broken down in situ. Previous controlled laboratory experiments carried out by our research group demonstrated that separately both photo-oxidation and cometabolism stimulate bacterial hydrocarbon degradation by natural bacterial assemblagesmore » collected from a chronically petroleum contaminated site in Bayboro Bay, Florida. Additionally, we also demonstrated that stable carbon and radiocarbon abundances of respired CO{sub 2} could be used to trace in situ hydrocarbon degradation by indigenous bacterial populations at this same site. This current proposal had two main objectives: (a) to evaluate the cumulative impact of cometabolism and photo-oxidation on hydrocarbon degradation by natural bacterial assemblages collected the same site in Bayboro Bay, Florida and (b) to determine if in situ hydrocarbon degradation by indigenous bacterial populations this site could be traced using natural radiocarbon and stable carbon abundances of assimilated bacterial carbon. Funds were used for 2 years of full support for one ESI Ph.D. student, April Croxton. To address our first objective a series of closed system bacterial incubations were carried out using photo-oxidized petroleum and pinfish (i.e. cometabolite). Bacterial production of CO{sub 2} was used as the indicator of hydrocarbon degradation and {delta}{sup 13}C analysis of the resultant CO{sub 2} was used to evaluate the source of the respired CO{sub 2} (i.e. petroleum hydrocarbons or the pinfish cometabolite). Results from these time series experiments demonstrated that short-term exposure of petroleum to UV light enhanced hydrocarbon degradation by 48% over that observed for non-photo-oxidized petroleum. Despite the greater bio-availability of the photo-oxidized over the non-photo-oxidized petroleum, an initial lag in CO{sub 2} production was observed indicating potential phototoxicity of the photo- by-products. {delta}{sup 13}C analysis and mass balance calculations reveal that co-metabolism with pinfish resulted in increased hydrocarbon degradation for both photo-oxidized and non-photo-oxidized petroleum each by over 100%. These results demonstrate the cumulative effect of photo-oxidation and co-metabolism on petroleum hydrocarbon degradation by natural bacterial populations indigenous to systems chronically impacted by hydrocarbon input. To address the second objective of this proposal bacterial concentrates were collected from Bayboro Harbor in April 2001 for nucleic acid extraction and subsequent natural radiocarbon abundance analyses. Unfortunately, however, all of these samples were lost due to a faulty compressor in our -70 freezer. The freezer was subsequently repaired and samples were again collected from Bayboro Harbor in June 2002 and again December 2002. Several attempts were made to extract the nucleic acid samples--however, the student was not able to successfully extract and an adequate amount of uncontaminated nucleic acid samples for subsequent natural radiocarbon abundance measurements of the bacterial carbon by accelerator mass spectrometry (i.e. require at least 50 {micro}g carbon for AMS measurement). Consequently, we were not able to address the second objective of this proposed work.« less

Bicarbonate stimulates the electron donation from Mn²⁺ to P₆₈₀⁺ in isolated D1/D2/cytochrome b559 complex.

PubMed

Zharmukhamedov, S K; Allakhverdiev, S I; Smolova, T N; Klimov, V V

2013-12-05

Influence of bicarbonate on the efficiency of the electron donation from Mn(2+) to P₆₈₀(+) in isolated D1/D2/cytochrome b559 complex was investigated. All the experiments were carried out in a medium depleted of HCO₃(-)/CO₂. Kinetics of photoinduced absorbance changes (ΔA) at different wavelengths and decrease of chlorophyll fluorescence yield (-ΔF) related to photoaccumulation of reduced pheophytin, the intermediary electron acceptor of photosystem II (PSII), in the presence of Mn(2+) under anaerobic conditions were measured. Addition of bicarbonate (1 mM) increased the amplitude of these ΔA and -ΔF at least by a factor of 3. Measurements of the photoinduced ΔA, related to photooxidation of the primary electron donor of PSII, chlorophyll P₆₈₀, were done in the presence of silicomolybdate as electron acceptor. These results show that the addition of 0.05 mM Mn(2+) alone or jointly with 1 mM bicarbonate induces a 20% and 70%-decrease of the magnitude of the ΔA at 680 nm. The effect of Mn(2+) (in the presence and absence of bicarbonate) was completely eliminated by the addition of 12 mM EDTA. All these bicarbonate effects were not observed if MgCl₂ or formate were used instead of MnCl₂ and bicarbonate, respectively. In the absence of Mn(2+), bicarbonate induced none of the mentioned above effects (increase of photoaccumulation of reduced pheophytin and decrease of photooxidation of P680). The presented data suggest that bicarbonate stimulates the electron donation from Mn(2+) to D1/D2/cyt b559 reaction center evidently due to formation of easily oxidizable Mn-bicarbonate complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

Heteroleptic monometallic and trimetallic ruthenium(II) complexes incorporating a π-extended dipyrrin ligand: Light-activated reactions with the A549 lung cancer cell line.

PubMed

Swavey, Shawn; Morford, Krista; Tsao, Max; Comfort, Kristen; Kilroy, Mary Kate

2017-10-01

A heteroleptic monometallic ruthenium(II) and a heteroleptic trimetallic ruthenium(II) complex have been synthesized and characterized. Both complexes have an overall 3+ charge, with the charge density greater for the monometallic complex. The electronic spectra of the monometallic ruthenium(II) complex exhibits intense π-π* transitions associated with the bipyridyl groups along with overlapping metal to ligand charge transfer (MLCT) and ligand centered π-π* transitions ranging from 520nm to approximately 600nm. The trimetallic ruthenium(II) complex, on the other hand, displays more well defined transitions with the expected π-π* transition of the bipyridyl groups at 294nm and Ru(dπ) to bpy(π*) MLCT transitions at 355nm and 502nm. In addition to these absorption bands an intense transition, 578nm, resulting from overlapping dipyrrin (π-π*) and Ru(dπ) to dipyrrin(π*) transitions is observed. Electrochemical and spectroelectrochemical experiments were used to help in assigning these transitions. Irradiation of the complexes in the presence of plasmid DNA within the photodynamic therapy window (600nm to 850nm) reveal, using electrophoresis, that both complexes are capable of causing photo-damage to the DNA backbone. The trimetallic ruthenium(II) complex; however, also shows the ability to generate photoinduced DNA damage in the absence of oxygen, suggesting a photo-oxidative process. Studies of the complexes toward lung cancer cells (A549 cell line) in the absence of light indicate little cytotoxicity up to 50μM. Upon irradiation of the cells with a low power 420nm light source the trimetallic complex showed considerably greater photo-cytotoxicity compared to the monometallic analog. A dose-dependent response curve gives an IC50 of 92μM for complex B. Copyright © 2017 Elsevier Inc. All rights reserved.

The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules.

PubMed

Fanchiotti, Brenda Gomes; Machado, Marcella Piffer Zamprogno; de Paula, Letícia Camilato; Durmuş, Mahmut; Nyokong, Tebello; da Silva Gonçalves, Arlan; da Silva, André Romero

2016-12-01

The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2-15μmol/L) were irradiated using a laser diode of 665nm with a power of 1-104mW and a light dose of 7.5J/cm 2 . The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1mW to 104mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104mW at 8μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8μmol/L while the increase from 2μmol/L to 5μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. Copyright © 2016 Elsevier B.V. All rights reserved.

Long-term photothermal/humidity testing of photovoltaic module polymer insulations and cover films

NASA Technical Reports Server (NTRS)

Mon, G.; Gonzales, C.; Willis, P.; Jetter, E.; Sugimura, R.

1990-01-01

The life expectancies of Tedlar and other polymer films considered for use as cover materials in terrestrial photovoltaic (PV) modules were investigated by exposing them for more than 13,000 h on an outdoor test stand and for up to 10,000 h in several accelerated multistress environments. Visual observations and diagnostic analyses of weight and mechanical strength losses were periodically conducted to assess the nature and rate of degradation of mechanical properties and to assess the effects of film thickness and UV stabilizer content. Spectroscopic analyses of pristine and degraded materials linked weight and mechanical property losses to the underlying photothermal/photooxidation chemistry. It is shown that heavy doses of UV stabilizers prolong, while elevated temperatures shorten, the useful life of these materials; humidity plays only a minor role. The most heavily UV-stabilized films are expected to operate usefully in a PV module front-cover application for only five to ten years. The performance of none of the tested films appears consistent with the 20-30 year life goals of the PV industry.

Biodegradation and photooxidation of crude oil under natural sunlight in the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Bacosa, H. P.; Erdner, D.; Liu, Z.

2016-02-01

An enormous amount of oil was observed in the deep and surface waters of the northern Gulf of Mexico (nGoM) following the Deepwater Horizon (DWH) spill. While the oil degradation and bacterial communities in the deep-sea plume have been widely investigated, the effect of sunlight on oil and bacterial assemblages in surface waters have received less attention. In this study, we amended surface water collected near the DWH site with crude oil and/or Corexit dispersant and incubated under natural sunlight in the nGoM for 36 d in summer of 2013. The residual alkanes, polycyclic aromatic hydrocarbons (PAHs), and alkalyted PAHs were analyzed by GC-MS, and bacterial community was determined via pyrosequencing. The results show that n-alkane biodegradation rate constants (first order) were ca. ten-fold higher than the photooxidation rate constants. While biodegradation was characterized by a lag phase, photooxidation rate constants for the 2-3 ring and 4-5 ring PAHs, were 0.08-0.98 day-1 and 0.01-0.07 day-1, respectively. Compared to biodegradation, photooxidation increased the transformation of 4-5 ring PAHs by 70% and 3-4 ring alkylated PAHs by 36%. Sunlight significantly reduced bacterial diversity and a driver of shifts in bacterial community structure in oil and Corexit treatments. In amended treatments, sunlight increased the relative abundances of Alteromonas, Marinobacter, Labrenzia, Sandarakinotalea, Halomonas and Bartonella, while the dark treatments enriched Thalassobius, Winogradskyella, Alcanivorax, Formosa, Eubacterium, Erythrobacter, Natronocella, and Pseudomonas. This suggests that different bacteria are degrading the hydrocarbons in the dark and under light exposure. In a follow up study using DNA-Stable isotope probing (SIP), we identified the alkane and PAH degraders using 13C-labeled hexadecane and phenanthrene, respectively. The results of metagenomic and metatranscriptomic analyses in the light and dark incubations will be presented. For the first time, we demonstrated the effects of sunlight in structuring microbial communities oil polluted water. This study provides quantitative measures of oil degradation under relevant field conditions, and improves our understanding of the role of sunlight on the fate of spilled oil and microbial community composition in the nGoM.

Perturbations in the Photosynthetic Pigment Status Result in Photooxidation-Induced Crosstalk between Carotenoid and Porphyrin Biosynthetic Pathways

PubMed Central

Park, Joon-Heum; Tran, Lien H.; Jung, Sunyo

2017-01-01

Possible crosstalk between the carotenoid and porphyrin biosynthetic pathways under photooxidative conditions was investigated by using their biosynthetic inhibitors, norflurazon (NF) and oxyfluorfen (OF). High levels of protoporphyrin IX (Proto IX) accumulated in rice plants treated with OF, whereas Proto IX decreased in plants treated with NF. Both NF and OF treatments resulted in greater decreases in MgProto IX, MgProto IX methyl ester, and protochlorophyllide. Activities and transcript levels of most porphyrin biosynthetic enzymes, particularly in the Mg-porphyrin branch, were greatly down-regulated in NF and OF plants. In contrast, the transcript levels of GSA, PPO1, and CHLD as well as FC2 and HO2 were up-regulated in NF-treated plants, while only moderate increases in FC2 and HO2 were observed in the early stage of OF treatment. Phytoene, antheraxanthin, and zeaxanthin showed high accumulation in NF-treated plants, whereas other carotenoid intermediates greatly decreased. Transcript levels of carotenoid biosynthetic genes, PSY1 and PDS, decreased in response to NF and OF, whereas plants in the later stage of NF treatment exhibited up-regulation of BCH and VDE as well as recovery of PDS. However, perturbed porphyrin biosynthesis by OF did not noticeably influence levels of carotenoid metabolites, regardless of the strong down-regulation of carotenoid biosynthetic genes. Both NF and OF plants appeared to provide enhanced protection against photooxidative damage, not only by scavenging of Mg-porphyrins, but also by up-regulating FC2, HO2, and Fe-chelatase, particularly with increased levels of zeaxanthin via up-regulation of BCH and VDE in NF plants. On the other hand, the up-regulation of GSA, PPO1, and CHLD under inhibition of carotenogenic flux may be derived from the necessity to recover impaired chloroplast biogenesis during photooxidative stress. Our study demonstrates that perturbations in carotenoid and porphyrin biosynthesis coordinate the expression of their biosynthetic genes to sustain plastid function at optimal levels by regulating their metabolic flux in plants under adverse stress conditions. PMID:29209351

Perturbations in the Photosynthetic Pigment Status Result in Photooxidation-Induced Crosstalk between Carotenoid and Porphyrin Biosynthetic Pathways.

PubMed

Park, Joon-Heum; Tran, Lien H; Jung, Sunyo

2017-01-01

Possible crosstalk between the carotenoid and porphyrin biosynthetic pathways under photooxidative conditions was investigated by using their biosynthetic inhibitors, norflurazon (NF) and oxyfluorfen (OF). High levels of protoporphyrin IX (Proto IX) accumulated in rice plants treated with OF, whereas Proto IX decreased in plants treated with NF. Both NF and OF treatments resulted in greater decreases in MgProto IX, MgProto IX methyl ester, and protochlorophyllide. Activities and transcript levels of most porphyrin biosynthetic enzymes, particularly in the Mg-porphyrin branch, were greatly down-regulated in NF and OF plants. In contrast, the transcript levels of GSA, PPO1 , and CHLD as well as FC2 and HO2 were up-regulated in NF-treated plants, while only moderate increases in FC2 and HO2 were observed in the early stage of OF treatment. Phytoene, antheraxanthin, and zeaxanthin showed high accumulation in NF-treated plants, whereas other carotenoid intermediates greatly decreased. Transcript levels of carotenoid biosynthetic genes, PSY1 and PDS , decreased in response to NF and OF, whereas plants in the later stage of NF treatment exhibited up-regulation of BCH and VDE as well as recovery of PDS . However, perturbed porphyrin biosynthesis by OF did not noticeably influence levels of carotenoid metabolites, regardless of the strong down-regulation of carotenoid biosynthetic genes. Both NF and OF plants appeared to provide enhanced protection against photooxidative damage, not only by scavenging of Mg - porphyrins, but also by up-regulating FC2, HO2 , and Fe-chelatase, particularly with increased levels of zeaxanthin via up-regulation of BCH and VDE in NF plants. On the other hand, the up-regulation of GSA, PPO1 , and CHLD under inhibition of carotenogenic flux may be derived from the necessity to recover impaired chloroplast biogenesis during photooxidative stress. Our study demonstrates that perturbations in carotenoid and porphyrin biosynthesis coordinate the expression of their biosynthetic genes to sustain plastid function at optimal levels by regulating their metabolic flux in plants under adverse stress conditions.

Fiber-optic Singlet Oxygen [1O2 (1Δg)] Generator Device Serving as a Point Selective Sterilizer

PubMed Central

Aebisher, David; Zamadar, Matibur; Mahendran, Adaickapillai; Ghosh, Goutam; McEntee, Catherine; Greer, Alexander

2016-01-01

Traditionally, Type II heterogeneous photo-oxidations produce singlet oxygen via external irradiation of a sensitizer and external supply of ground-state oxygen. A potential improvement is reported here. A hollow-core fiber-optic device was developed with an “internal” supply of light and flowing oxygen, and a porous photosensitizer-end capped configuration. Singlet oxygen was delivered through the fiber tip. The singlet oxygen steady-state concentration in the immediate vicinity of the probe tip was ca 20 fM by N-benzoyl-DL-methionine trapping. The device is portable and the singlet oxygen-generating tip is maneuverable, which opened the door to simple disinfectant studies. Complete Escherichia coli inactivation was observed in 2 h when the singlet oxygen sensitizing probe tip was immersed in 0.1 mL aqueous samples of 0.1–4.4 × 107 cells. Photobleaching of the probe tip occurred after ca 12 h of use, requiring baking and sensitizer reloading steps for reuse. PMID:20497367

The functional significance of black-pigmented leaves: photosynthesis, photoprotection and productivity in Ophiopogon planiscapus 'Nigrescens'.

PubMed

Hatier, Jean-Hugues B; Clearwater, Michael J; Gould, Kevin S

2013-01-01

Black pigmented leaves are common among horticultural cultivars, yet are extremely rare across natural plant populations. We hypothesised that black pigmentation would disadvantage a plant by reducing photosynthesis and therefore shoot productivity, but that this trait might also confer protective benefits by shielding chloroplasts against photo-oxidative stress. CO2 assimilation, chlorophyll a fluorescence, shoot biomass, and pigment concentrations were compared for near isogenic green- and black-leafed Ophiopogonplaniscapus 'Nigrescens'. The black leaves had lower maximum CO2 assimilation rates, higher light saturation points and higher quantum efficiencies of photosystem II (PSII) than green leaves. Under saturating light, PSII photochemistry was inactivated less and recovered more completely in the black leaves. In full sunlight, green plants branched more abundantly and accumulated shoot biomass quicker than the black plants; in the shade, productivities of the two morphs were comparable. The data indicate a light-screening, photoprotective role of foliar anthocyanins. However, limitations to photosynthetic carbon assimilation are relatively small, insufficient to explain the natural scarcity of black-leafed plants.

Potato Annexin STANN1 Promotes Drought Tolerance and Mitigates Light Stress in Transgenic Solanum tuberosum L. Plants.

PubMed

Szalonek, Michal; Sierpien, Barbara; Rymaszewski, Wojciech; Gieczewska, Katarzyna; Garstka, Maciej; Lichocka, Malgorzata; Sass, Laszlo; Paul, Kenny; Vass, Imre; Vankova, Radomira; Dobrev, Peter; Szczesny, Pawel; Marczewski, Waldemar; Krusiewicz, Dominika; Strzelczyk-Zyta, Danuta; Hennig, Jacek; Konopka-Postupolska, Dorota

2015-01-01

Annexins are a family of calcium- and membrane-binding proteins that are important for plant tolerance to adverse environmental conditions. Annexins function to counteract oxidative stress, maintain cell redox homeostasis, and enhance drought tolerance. In the present study, an endogenous annexin, STANN1, was overexpressed to determine whether crop yields could be improved in potato (Solanum tuberosum L.) during drought. Nine potential potato annexins were identified and their expression characterized in response to drought treatment. STANN1 mRNA was constitutively expressed at a high level and drought treatment strongly increased transcription levels. Therefore, STANN1 was selected for overexpression analysis. Under drought conditions, transgenic potato plants ectopically expressing STANN1 were more tolerant to water deficit in the root zone, preserved more water in green tissues, maintained chloroplast functions, and had higher accumulation of chlorophyll b and xanthophylls (especially zeaxanthin) than wild type (WT). Drought-induced reductions in the maximum efficiency and the electron transport rate of photosystem II (PSII), as well as the quantum yield of photosynthesis, were less pronounced in transgenic plants overexpressing STANN1 than in the WT. This conferred more efficient non-photochemical energy dissipation in the outer antennae of PSII and probably more efficient protection of reaction centers against photooxidative damage in transgenic plants under drought conditions. Consequently, these plants were able to maintain effective photosynthesis during drought, which resulted in greater productivity than WT plants despite water scarcity. Although the mechanisms underlying this stress protection are not yet clear, annexin-mediated photoprotection is probably linked to protection against light-induced oxidative stress.

Potato Annexin STANN1 Promotes Drought Tolerance and Mitigates Light Stress in Transgenic Solanum tuberosum L. Plants

PubMed Central

Szalonek, Michal; Sierpien, Barbara; Rymaszewski, Wojciech; Gieczewska, Katarzyna; Garstka, Maciej; Lichocka, Malgorzata; Sass, Laszlo; Paul, Kenny; Vass, Imre; Vankova, Radomira; Dobrev, Peter; Szczesny, Pawel; Marczewski, Waldemar; Krusiewicz, Dominika; Strzelczyk-Zyta, Danuta; Hennig, Jacek; Konopka-Postupolska, Dorota

2015-01-01

Annexins are a family of calcium- and membrane-binding proteins that are important for plant tolerance to adverse environmental conditions. Annexins function to counteract oxidative stress, maintain cell redox homeostasis, and enhance drought tolerance. In the present study, an endogenous annexin, STANN1, was overexpressed to determine whether crop yields could be improved in potato (Solanum tuberosum L.) during drought. Nine potential potato annexins were identified and their expression characterized in response to drought treatment. STANN1 mRNA was constitutively expressed at a high level and drought treatment strongly increased transcription levels. Therefore, STANN1 was selected for overexpression analysis. Under drought conditions, transgenic potato plants ectopically expressing STANN1 were more tolerant to water deficit in the root zone, preserved more water in green tissues, maintained chloroplast functions, and had higher accumulation of chlorophyll b and xanthophylls (especially zeaxanthin) than wild type (WT). Drought-induced reductions in the maximum efficiency and the electron transport rate of photosystem II (PSII), as well as the quantum yield of photosynthesis, were less pronounced in transgenic plants overexpressing STANN1 than in the WT. This conferred more efficient non-photochemical energy dissipation in the outer antennae of PSII and probably more efficient protection of reaction centers against photooxidative damage in transgenic plants under drought conditions. Consequently, these plants were able to maintain effective photosynthesis during drought, which resulted in greater productivity than WT plants despite water scarcity. Although the mechanisms underlying this stress protection are not yet clear, annexin-mediated photoprotection is probably linked to protection against light-induced oxidative stress. PMID:26172952

FTIR analysis on aging characteristics of ABS/PC blend under UV-irradiation in air

NASA Astrophysics Data System (ADS)

Li, Jiarong; Chen, Fu; Yang, Long; Jiang, Long; Dan, Yi

2017-09-01

Fourier Transform Infrared Spectroscopy (FTIR) is adopted to study the aging characteristics of poly(acrylonitrile-butadiene-styrene)/polycarbonate (ABS/PC) blend under UV-irradiation in air by analyzing the variation of the three main absorbance at about 967 cm- 1, 1720 cm- 1 and 3420 cm- 1 associated with carbon-hydrogen bonds belonging to 1,4 butadiene, carbonyl and hydroxyl groups, respectively. Results indicate that, under UV-irradiation in air, the photo-oxidation of the blend is not a simple combination of the photo-oxidation of corresponding ABS and PC themselves and takes place predominantly at the ABS component. Due to the interaction between the two components and the Fries rearrangement taken place in the PC component during the UV-irradiation in air, the ABS/PC blends behave higher photo-stability than ABS has.

FM Dye Photo-Oxidation as a Tool for Monitoring Membrane Recycling in Inner Hair Cells

PubMed Central

Rizzoli, Silvio O.

2014-01-01

Styryl (FM) dyes have been used for more than two decades to investigate exo- and endocytosis in conventional synapses. However, they are difficult to use in the inner hair cells of the auditory pathway (IHCs), as FM dyes appear to penetrate through mechanotransducer channels into the cytosol of IHCs, masking endocytotic uptake. To solve this problem we applied to IHCs the FM dye photo-oxidation technique, which renders the dyes into electron microscopy markers. Photo-oxidation allowed the unambiguous identification of labeled organelles, despite the presence of FM dye in the cytosol. This enabled us to describe the morphologies of several organelles that take up membrane in IHCs, both at rest and during stimulation. At rest, endosome-like organelles were detected in the region of the cuticular plate. Larger tubulo-cisternal organelles dominated the top and nuclear regions. Finally, the basal region, where the IHC active zones are located, contained few labeled organelles. Stimulation increased significantly membrane trafficking in the basal region, inducing the appearance of labeled vesicles and cistern-like organelles. The latter were replaced by small, synaptic-like vesicles during recovery after stimulation. In contrast, no changes in membrane trafficking were induced by stimulation in the cuticular plate region or in the top and nuclear regions. We conclude that synaptic vesicle recycling takes place mostly in the basal region of the IHCs. Other organelles participate in abundant constitutive membrane trafficking throughout the rest of the IHC volume. PMID:24505482

SOA formation from photooxidation of naphthalene and methylnaphthalenes with m-xylene and surrogate mixtures

NASA Astrophysics Data System (ADS)

Chen, Chia-Li; Li, Lijie; Tang, Ping; Cocker, David R.

2018-05-01

SOA formation is not well predicted in current models in urban area. The interaction among multiple anthropogenic volatile organic compounds is essential for the SOA formation in the complex urban atmosphere. Secondary organic aerosol (SOA) from the photooxidation of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene as well as individual polycyclic aromatic hydrocarbons (PAHs) mixed with m-xylene or an atmospheric surrogate mixture was explored in the UCR CE-CERT environmental chamber under urban relevant low NOx and extremely low NOx (H2O2) conditions. Addition of m-xylene suppressed SOA formation from the individual PAH precursor. A similar suppression effect on SOA formation was observed during the surrogate mixture photooxidation suggesting the importance of gas-phase chemical reactivity to SOA formation. The SOA growth rate for different PAH-m-xylene mixtures was strongly correlated with initial [HO2]/[RO2] ratio but negatively correlated with initial m-xylene/NO ratio. Decreasing SOA formation was observed for increasing m-xylene/PAHs ratios and increasing initial m-xylene/NO ratio. The SOA chemical composition characteristics such as f44 versus f43, H/C ratio, O/C ratio, and the oxidation state of the carbon OSbarc were consistent with a continuously aging with the SOA exhibiting characteristics of both individual precursors. SOA formation from PAHs was also suppressed within an atmospheric surrogate mixture compared to the SOA formed from individual PAHs, indicating that atmospheric reactivity directly influences SOA formation from PAHs.

Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes

NASA Astrophysics Data System (ADS)

Riva, Matthieu; Da Silva Barbosa, Thais; Lin, Ying-Hsuan; Stone, Elizabeth A.; Gold, Avram; Surratt, Jason D.

2016-09-01

We report the formation of aliphatic organosulfates (OSs) in secondary organic aerosol (SOA) from the photooxidation of C10-C12 alkanes. The results complement those from our laboratories reporting the formation of OSs and sulfonates from gas-phase oxidation of polycyclic aromatic hydrocarbons (PAHs). Both studies strongly support the formation of OSs from the gas-phase oxidation of anthropogenic precursors, as hypothesized on the basis of recent field studies in which aromatic and aliphatic OSs were detected in fine aerosol collected from several major urban locations. In this study, dodecane, cyclodecane and decalin, considered to be important SOA precursors in urban areas, were photochemically oxidized in an outdoor smog chamber in the presence of either non-acidified or acidified ammonium sulfate seed aerosol. Effects of acidity and relative humidity on OS formation were examined. Aerosols collected from all experiments were characterized by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS). Most of the OSs identified could be explained by formation of gaseous epoxide precursors with subsequent acid-catalyzed reactive uptake onto sulfate aerosol and/or heterogeneous reactions of hydroperoxides. The OSs identified here were also observed and quantified in fine urban aerosol samples collected in Lahore, Pakistan, and Pasadena, CA, USA. Several OSs identified from the photooxidation of decalin and cyclodecane are isobars of known monoterpene organosulfates, and thus care must be taken in the analysis of alkane-derived organosulfates in urban aerosol.

Permeability of DOPC bilayers under photoinduced oxidation: Sensitivity to photosensitizer.

PubMed

Bacellar, Isabel O L; Baptista, Mauricio S; Junqueira, Helena C; Wainwright, Mark; Thalmann, Fabrice; Marques, Carlos M; Schroder, André P

2018-06-07

The modification of lipid bilayer permeability is one of the most striking yet poorly understood physical transformations that follow photoinduced lipid oxidation. We have recently proposed that the increase of permeability of photooxidized 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers is controlled by the time required by the oxidized lipid species to diffuse and aggregate into pores. Here we further probe this mechanism by studying photosensitization of DOPC membranes by methylene blue (MB) and DO15, a more hydrophobic phenothiazinium photosensitizer, under different irradiation powers. Our results not only reveal the interplay between the production rate and the diffusion of the oxidized lipids, but highlight also the importance of photosensitizer localization in the kinetics of oxidized membrane permeability. Copyright © 2018. Published by Elsevier B.V.

Effect of Reprocessing and Accelerated Weathering on Impact-Modified Recycled Blend

NASA Astrophysics Data System (ADS)

Ramesh, V.; Mohanty, Smita; Biswal, Manoranjan; Nayak, Sanjay K.

2015-12-01

Recovery of recycled polycarbonate, acrylonitrile butadiene styrene, high-impact polystyrene, and its blends from waste electrical and electronic equipment plastics products properties were enhanced by the addition of virgin polycarbonate and impact modifier. The optimized blend formulation was processed through five cycles, at processing temperature, 220-240 °C and accelerated weathering up to 700 h. Moreover, the effect of reprocessing and accelerated weathering in the physical properties of the modified blends was investigated by mechanical, thermal, rheological, and morphological studies. The results show that in each reprocessing cycle, the tensile strength and impact strength decreased significantly and the similar behavior has been observed from accelerated weathering. Subsequently, the viscosity decreases and this decrease becomes the effect of thermal and photo-oxidative degradation. This can be correlated with FTIR analysis.

The active centre of triose phosphate isomerase

PubMed Central

Burton, Pamela M.; Waley, S. G.

1966-01-01

The molecular weight and amino acid composition of triose phosphate isomerase have been determined. The molecular weight (43000) is lower and the molecular activity (500000) higher than those of most other glycolytic enzymes. Reaction with iodoacetate (studied with radioactive reagent) takes place in two phases: in the first phase, at pH6·3, cysteine and methionine groups react and enzymic activity is unimpaired; in the second phase, histidine reacts and enzymic activity is lost. Photo-oxidation leads to inactivation, with loss of cysteine, of histidine and of tryptophan, but little loss of tyrosine. The mechanism postulated for the action of the enzyme demands the intervention of a group functioning as a base, and the results obtained are consistent with histidine's being the basic group in the active centre. PMID:5969283

Surface Chemistry of Nano-Structured Mixed Metal Oxide Films

DTIC Science & Technology

2012-12-11

surface chemical and catalytic properties of the films, and finally (iv) we also investigated some of these materials as electrodes for the photo-oxidation of water and as anode materials for lithium ion batteries .

Direct evidence for coastal iodine particles from Laminaria macroalgae - linkage to emissions of molecular iodine

NASA Astrophysics Data System (ADS)

McFiggans, G.; Coe, H.; Burgess, R.; Allan, J.; Cubison, M.; Rami Alfarra, M.; Saunders, R.; Saiz-Lopez, A.; Plane, J. M. C.; Wevill, D.; Carpenter, L.; Rickard, A. R.; Monks, P. S.

2004-02-01

Renewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O'Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical and behave alike when exposed to increased humidity environments. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed.

Enhanced photoprotection by protein-bound vs free xanthophyll pools: a comparative analysis of chlorophyll b and xanthophyll biosynthesis mutants.

PubMed

Dall'Osto, Luca; Cazzaniga, Stefano; Havaux, Michel; Bassi, Roberto

2010-05-01

When light absorbed by plants exceeds the capacity of photosynthesis, the xanthophyll violaxanthin is reversibly de-epoxidized to zeaxanthin in the so-called xanthophyll cycle. Zeaxanthin plays a key role in the protection of photosynthetic organisms against excess light, by promoting rapidly reversible (qE) and long-term (qI) quenching of excited chlorophylls, and preventing lipid oxidation. The photoprotective role of zeaxanthin, either free or bound to light-harvesting complexes (Lhcs), has been investigated by using mutants lacking Chl b (ch1) and/or specific xanthophyll species (npq, lut2). The ch1 mutation causes (1) the absence of Lhcb proteins; (2) strong reduction of the feedback de-excitation (qE); and (3) accumulation of xanthophylls as free pigments into thylakoids. Ch1 mutants showed extreme sensitivity to photo-oxidative stress in high light, due to higher singlet oxygen (¹O₂) release. The double mutant ch1npq1 was more sensitive to photo-oxidation than ch1, showing that zeaxanthin does protect lipids even when free in the membrane. Nevertheless, lack of zeaxanthin had a much stronger impact on the level of lipid peroxidation in Lhcs-containing plants (WT vs npq1) with respect to Lhc-less plants (ch1 vs ch1npq1), implying that its protective effect is enhanced by interaction with antenna proteins. It is proposed that the antioxidant capacity of zeaxanthin is empowered in the presence of PSII-LHCs-Zea complexes, while its effect on enhancement of qE only provides a minor contribution. Comparison of the sensitivity of WT vs npq1 plants to exogenous ¹O₂ suggests that besides the scavenging of ¹O₂, at least one additional mechanism is involved in chloroplast photoprotection.

Develop Silicone Encapsulation Systems for Terrestrial Silicon Solar Arrays

NASA Technical Reports Server (NTRS)

1979-01-01

A cost effective encapsulant system was identified and a silicone acrylic cover material containing a durable ultraviolet screening agent was prepared. The effectiveness of the cover material in protecting photo-oxidatively sensitive polymers was demonstrated.

SURFACTANT ENHANCED PHOTO-OXIDATION OF WASTEWATERS

EPA Science Inventory

Initial research projects using the nonionic surfactant Brij-35 established that this surfactant could successfully adsolublize aromatic organic pollutants such as anthracene, naphthalene, benzoic acid, chlorophenol, and benzene onto the surface of TiO₂ par...

Photooxidative desulfurization for diesel using Fe / N - TiO2 photocatalyst

NASA Astrophysics Data System (ADS)

Khan, Muhammad Saqib; Kait, Chong Fai; Mutalib, Mohd Ibrahim Abdul

2014-10-01

A series of N - TiO2 with different mol% N was synthesized via sol-gel method and characterized using thermal gravimetric analyzer and raman spectroscopy. 0.2 wt% Fe was incorporated onto the calcined (200°C) N - TiO2 followed by calcination at 200°C, 250°C and 300°C. Photooxidative desulfurization was conducted in the presence of 0.2wt% Fe / N - TiO2 with different mol% N with and without oxidant (H2O2). Oxidative desulfurization was only achieved when H2O2 was used while without H2O2 no major effect on the sulfur removal. 0.2Fe -30N - H2O2 photocatalysts showed best performance at all calcination temperatures as compared to other mol% N - H2O2 photocatalysts. 16.45% sulfur removal was achieved using photocatalysts calcined at 300 °C.

Integrated photooxidative extractive deep desulfurization using metal doped TiO2 and eutectic based ionic liquid

NASA Astrophysics Data System (ADS)

Zaid, Hayyiratul Fatimah Mohd; Kait, Chong Fai; Mutalib, Mohamed Ibrahim Abdul

2016-11-01

A series of metal doped TiO2 namely Fe/TiO2, Cu/TiO2 and Cu-Fe/TiO2 were synthesized and characterized, to be used as a photocatalyst in the integrated photooxidative extractive deep desulfurization for model oil (dodecane) and diesel fuel. The order of the photocatalytic activity was Cu-Fe/TiO2 followed by Cu/TiO2 and then Fe/TiO2. Cu-Fe/TiO2 was an effective photocatalyst for sulfur conversion at ambient atmospheric pressure. Hydrogen peroxide was used as the source of oxidant and eutectic-based ionic liquid as the extractant. Sulfur conversion in model oil reached 100%. Removal of sulfur from model oil was done by two times extraction with a removal of 97.06% in the first run and 2.94% in the second run.

Photo-oxidation of PAHs with calcium peroxide as a source of the hydroxyl radicals

NASA Astrophysics Data System (ADS)

Kozak, Jolanta; Włodarczyk-Makuła, Maria

2018-02-01

The efficiency of the removal of selected PAHs from the pretreated coking wastewater with usage of CaO2, Fenton reagent (FeSO4) and UV rays are presented in this article. The investigations were carried out using coking wastewater originating from biological, industrial wastewater treatment plant. At the beginning of the experiment, the calcium peroxide (CaO2) powder as a source of hydroxyl radicals (OH•) and Fenton reagent were added to the samples of wastewater. Then, the samples were exposed to UV rays for 360 s. The process was carried out at pH 3.5-3.8. After photo-oxidation process a decrease in the PAHs concentration was observed. The removal efficiency of selected hydrocarbons was in the ranged of 89-98%. The effectiveness of PAHs degradation was directly proportional to the calcium peroxide dose.

Intact Plastids Are Required for Nitrate- and Light-Induced Accumulation of Nitrate Reductase Activity and mRNA in Squash Cotyledons 1

PubMed Central

Oelmüller, Rolf; Briggs, Winslow R.

1990-01-01

Induction of nitrate reductase activity and mRNA by nitrate and light is prevented if chloroplasts are destroyed by photooxidation in norflurazon-treated squash (Cucurbita maxima L.) cotyledons. The enzyme activity and mRNA can be induced if norflurazon-treated squash seedlings are kept in low-intensity red light, which minimizes photodamage to the plastids. It is concluded that induction of nitrate reductase activity and nitrate reductase mRNA requires intact plastids. If squash seedlings grown in low-intensity red light are transferred to photooxidative white light, nitrate reductase activity accumulates during the first 12 hours after the shift and declines thereafter. Thus photodamage to the plastids and the disappearance of nitrate reductase activity and mRNA are events separable in time, and disappearance of the enzyme activity is a consequence of the damage to the plastids. Images Figure 1 Figure 3 Figure 4 PMID:16667294

Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO₂(110) in photooxidation using density functional theory calculations with hybrid functional.

PubMed

Wang, Dong; Wang, Haifeng; Hu, P

2015-01-21

Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

Polydiacetylene as an all-optical picosecond Switch

NASA Technical Reports Server (NTRS)

Abdeldayem, Hossin A.; Frazier, D. O.; Paley, M. S.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Polydiacetylene derivative of 2-methyl-4-nitroaniline (PDAMNA) shows a picosecond switching property, which illustrated a partial all-optical picosecond NAND logic gate. The switching phenomenon was demonstrated by waveguiding two collinear beams at 633 nm and 532 nm through a hollow fiber of 50 micrometers diameter, coated from inside with a thin film of PDAMNA. A Z-scan investigations of a PDAMNA thin film on quartz substrate revealed that the switching effect was attributed to an excited state absorption in the systems. The studies also showed that the polymer suffers a photo-oxidation beyond an intensity level of 2.9 x 10(exp 6) w/square cm. The photo-oxidized film has different physical properties that are different from the original film before oxidation. The life time of both excited states before and after oxidation as well as their absorption coefficients were estimated by fitting a three level system model to the experimental results.

Tryptophan and kynurenine determination in human hair by liquid chromatography.

PubMed

Dario, Michelli F; Freire, Thamires Batello; Pinto, Claudinéia Aparecida Sales de Oliveira; Prado, María Segunda Aurora; Baby, André R; Velasco, Maria Valéria R

2017-10-15

Tryptophan, an amino acid found in hair proteinaceous structure is used as a marker of hair photodegradation. Also, protein loss caused by several chemical/physical treatments can be inferred by tryptophan quantification. Kynurenine is a photo-oxidation product of tryptophan, expected to be detected when hair is exposed mainly to UVB (290-320nm) radiation range. Tryptophan from hair is usually quantified directly as a solid or after alkaline hydrolysis, spectrofluorimetrically. However, these types of measure are not sufficiently specific and present several interfering substances. Thus, this work aimed to propose a quantification method for both tryptophan and kynurenine in hair samples, after alkali hydrolysis process, by using high-performance liquid chromatography (HPLC) with fluorimetric and UV detection. The tryptophan and kynurenine quantification method was developed and validated. Black, white, bleached and dyed (blond and auburn) hair tresses were used in this study. Tryptophan and kynurenine were separated within ∼9min by HPLC. Both black and white virgin hair samples presented similar concentrations of tryptophan, while bleaching caused a reduction in the tryptophan content as well as dyeing process. Unexpectedly, UV/vis radiation did not promote significantly the conversion of tryptophan into its photo-oxidation product and consequently, kynurenine was not detected. Thus, this works presented an acceptable method for quantification of tryptophan and its photooxidation metabolite kynurenine in hair samples. Also, the results indicated that bleaching and dyeing processes promoted protein/amino acids loss but tryptophan is not extensively degraded in human hair by solar radiation. Copyright © 2017 Elsevier B.V. All rights reserved.

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes.

PubMed

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-07-21

This study deals with the exploration of NixCo₁-xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co₀.₄Ni₀.₆Fe₂O₄ (154.02 m(2) g(-1)). Co₀.₄Ni₀.₆Fe₂O₄ showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe₂O₄ was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH₄ on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni(2+) in to the cobalt ferrite lattice due to octahedral site preference of Ni(2+). Almost 99% degradation was achieved in 20 min using NiFe₂O₄ nanoparticles as catalyst.

FORMATION OF POLYKETONES IN IRRADIATED TOLUENE/PROPYLENE/NOX/AIR MIXTURES

EPA Science Inventory

A laboratory study was carried out to investigate the formation of polyketones in secondary organic aerosol from photooxidation of the aromatic hydrocarbon toluene, a major constituent of automobile exhaust. The laboratory experiments consisted of irradiating toluene/propylene...

Gas-phase Precursors to Anthropogenic SOA: Using the MCM to Probe Detailed Observations of Aromatic Photo-oxidation

NASA Astrophysics Data System (ADS)

Rickard, A. R.; Wyche, K. P.; Metzger, A.; Monks, P. S.; Ellis, A. M.; Baltensperger, U.; Pilling, M. J.; Jenkin, M. E.

2008-12-01

The formation of photochemical ozone and particulate matter are major priorities in the determination of European air quality policies. Predictions of the future state of the atmosphere and the development of appropriate mitigation strategies rely on models, which necessarily incorporate chemistry. The Master Chemical Mechanism (MCM, http://mcm.leeds.ac.uk/MCM) is a near-explicit chemical mechanism originally conceived to model ozone formation in Europe but now also employed as a benchmark mechanism in a wide variety of applications where chemical detail is required. The MCM currently describes the detailed gas- phase tropospheric degradation of a 135 primary emitted volatile organic compounds (VOCs) leading to a mechanism containing ca. 5900 species and 13500 reactions. In order that the MCM continues to be a state-of-the-art resource for the atmospheric science community it resides under a constant regime of evaluation, development and improvement. Individual VOC photochemical mechanisms are evaluated using data obtained, under a variety of atmospheric conditions, from highly instrumented smog chambers. Smog chamber experiments are crucial, not only for mechanism evaluation, but also for mechanism development. Findings obtained from combined model and chamber studies can additionally provide key insight for guiding the directions of future laboratory experiments. Recently, the MCM was updated to MCMv3.1 in order to take into account recent advancements in the understanding of aromatic photo-oxidation, an important class of anthropogenic VOCs. As well as constituting precursors to secondary organic aerosol (SOA), aromatics generally have high photochemical ozone creation potentials (POCPs) and hence contribute significantly towards tropospheric ozone formation. In the work presented, a detailed gas-phase photochemical chamber box model, incorporating the MCMv3.1 degradation mechanism for 1,3,5-trimethylbenzene (TMB), has been used to simulate data measured during a series of chamber experiments carried out at the Paul Scherrer Institute Aerosol Chamber in order to evaluate the mechanism under a variety of VOC/NOx conditions. More specifically, the model was used in the interpretation of data recorded by the University of Leicester's Chemical Ionisation Reaction Time-of- Flight Mass Spectrometer (CIR-TOF-MS), a novel instrument used to provide comprehensive, high (mass and time) resolution measurements of the organic gaseous oxidation products formed from the TMB precursor. Additional supporting gas and aerosol measurements also enable us to explore the "missing link" between the gas and aerosol phases. Model-measurement comparisons have been used to gain an insight into the complex array of oxygenated products formed, including the peroxide bicyclic ring opening products (gamma-dicarbonyls and furanones) and the O2-bridged peroxide bicyclic ring retaining products (diol, ketone and nitrate). To our knowledge this is the first time these O2-bridged species have been identified in the gas-phase. The model was also used to give insights into which gas-phase species were participating in SOA formation, with the primary and secondary peroxide products, formed primarily under NOx-limiting conditions ([NO] approaches zero), identified as likely candidates.

Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water

PubMed Central

Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F. Y.; Luan, Tiangang

2015-01-01

Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment. PMID:26239357

Enhancing the efficacy of cytotoxic agents for cancer therapy using photochemical internalisation

PubMed Central

Moore, Caroline M.; Loizidou, Marilena; MacRobert, Alexander J.; Woodhams, Josephine H.

2016-01-01

Photochemical internalisation (PCI) is a technique for improving cellular delivery of certain bioactive agents which are prone to sequestration within endolysosomes. There is a wide range of agents suitable for PCI‐based delivery including toxins, oligonucleotides, genes and immunoconjugates which demonstrates the versatility of this technique. The basic mechanism of PCI involves triggering release of the agent from endolysosomes within the target cells using a photosensitiser which is selectively retained with the endolysosomal membranes. Excitation of the photosensitiser by visible light leads to disruption of the membranes via photooxidative damage thereby releasing the agent into the cytosol. This treatment enables the drugs to reach their intended subcellular target more efficiently and improves their efficacy. In this review we summarise the applications of this technique with the main emphasis placed on cancer chemotherapy. PMID:25758607

Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses.

PubMed

Suga, Michihiro; Akita, Fusamichi; Hirata, Kunio; Ueno, Go; Murakami, Hironori; Nakajima, Yoshiki; Shimizu, Tetsuya; Yamashita, Keitaro; Yamamoto, Masaki; Ago, Hideo; Shen, Jian-Ren

2015-01-01

Photosynthesis converts light energy into biologically useful chemical energy vital to life on Earth. The initial reaction of photosynthesis takes place in photosystem II (PSII), a 700-kilodalton homodimeric membrane protein complex that catalyses photo-oxidation of water into dioxygen through an S-state cycle of the oxygen evolving complex (OEC). The structure of PSII has been solved by X-ray diffraction (XRD) at 1.9 ångström resolution, which revealed that the OEC is a Mn4CaO5-cluster coordinated by a well defined protein environment. However, extended X-ray absorption fine structure (EXAFS) studies showed that the manganese cations in the OEC are easily reduced by X-ray irradiation, and slight differences were found in the Mn-Mn distances determined by XRD, EXAFS and theoretical studies. Here we report a 'radiation-damage-free' structure of PSII from Thermosynechococcus vulcanus in the S1 state at a resolution of 1.95 ångströms using femtosecond X-ray pulses of the SPring-8 ångström compact free-electron laser (SACLA) and hundreds of large, highly isomorphous PSII crystals. Compared with the structure from XRD, the OEC in the X-ray free electron laser structure has Mn-Mn distances that are shorter by 0.1-0.2 ångströms. The valences of each manganese atom were tentatively assigned as Mn1D(III), Mn2C(IV), Mn3B(IV) and Mn4A(III), based on the average Mn-ligand distances and analysis of the Jahn-Teller axis on Mn(III). One of the oxo-bridged oxygens, O5, has significantly longer distances to Mn than do the other oxo-oxygen atoms, suggesting that O5 is a hydroxide ion instead of a normal oxygen dianion and therefore may serve as one of the substrate oxygen atoms. These findings provide a structural basis for the mechanism of oxygen evolution, and we expect that this structure will provide a blueprint for the design of artificial catalysts for water oxidation.

PHOTOOXIDATION OF HG(0) IN AN ESTUARINE SYSTEM. (R827915)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Lutein and brain function

USDA-ARS?s Scientific Manuscript database

Lutein is one of the most prevalent carotenoids in nature and in the human diet. Together with zeaxanthin, it is highly concentrated in macular pigment in the foveal retina of primates, attenuating blue light exposure, providing protection from photo-oxidation and enhancing visual performance. Rece...

TIO2 ADVANCED PHOTO-OXIDATION TECHNOLOGY: EFFECT OF ELECTRON ACCEPTORS

EPA Science Inventory

The effects of electron acceptors (additives) such as hydrogen peroxide, ammonium persulphate, potassium bromate and potassium peroxymonosulphate (ozone) on the TiO2 photocatalytic degradation of various organic pollutants were examined at various conditions. he individual and th...

The Functional Significance of Black-Pigmented Leaves: Photosynthesis, Photoprotection and Productivity in Ophiopogon planiscapus ‘Nigrescens’

PubMed Central

Hatier, Jean-Hugues B.; Clearwater, Michael J.; Gould, Kevin S.

2013-01-01

Black pigmented leaves are common among horticultural cultivars, yet are extremely rare across natural plant populations. We hypothesised that black pigmentation would disadvantage a plant by reducing photosynthesis and therefore shoot productivity, but that this trait might also confer protective benefits by shielding chloroplasts against photo-oxidative stress. CO2 assimilation, chlorophyll a fluorescence, shoot biomass, and pigment concentrations were compared for near isogenic green- and black-leafed Ophiopogon planiscapus ‘Nigrescens’. The black leaves had lower maximum CO2 assimilation rates, higher light saturation points and higher quantum efficiencies of photosystem II (PSII) than green leaves. Under saturating light, PSII photochemistry was inactivated less and recovered more completely in the black leaves. In full sunlight, green plants branched more abundantly and accumulated shoot biomass quicker than the black plants; in the shade, productivities of the two morphs were comparable. The data indicate a light-screening, photoprotective role of foliar anthocyanins. However, limitations to photosynthetic carbon assimilation are relatively small, insufficient to explain the natural scarcity of black-leafed plants. PMID:23826347

Time-resolved vibrational spectroscopy detects protein-based intermediates in the photosynthetic oxygen-evolving cycle.

PubMed

Barry, Bridgette A; Cooper, Ian B; De Riso, Antonio; Brewer, Scott H; Vu, Dung M; Dyer, R Brian

2006-05-09

Photosynthetic oxygen production by photosystem II (PSII) is responsible for the maintenance of aerobic life on earth. The production of oxygen occurs at the PSII oxygen-evolving complex (OEC), which contains a tetranuclear manganese (Mn) cluster. Photo-induced electron transfer events in the reaction center lead to the accumulation of oxidizing equivalents on the OEC. Four sequential photooxidation reactions are required for oxygen production. The oxidizing complex cycles among five oxidation states, called the S(n) states, where n refers to the number of oxidizing equivalents stored. Oxygen release occurs during the S(3)-to-S(0) transition from an unstable intermediate, known as the S(4) state. In this report, we present data providing evidence for the production of an intermediate during each S state transition. These protein-derived intermediates are produced on the microsecond to millisecond time scale and are detected by time-resolved vibrational spectroscopy on the microsecond time scale. Our results suggest that a protein-derived conformational change or proton transfer reaction precedes Mn redox reactions during the S(2)-to-S(3) and S(3)-to-S(0) transitions.

PHOTOOXIDATION OF HG(0) IN ARTIFICIAL AND NATURAL WATERS. (R827915)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

EPA Science Inventory

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evalua...

Physiological and leaf metabolome changes in the xerohalophyte species Atriplex halimus induced by salinity.

PubMed

Bendaly, Alia; Messedi, Dorsaf; Smaoui, Abderrazak; Ksouri, Riadh; Bouchereau, Alain; Abdelly, Chedly

2016-06-01

Atriplex halimus is a xerohalophyte plant, which could be used as cash crops. This plant was integrated in Tunisian government programs the aim of which is to rehabilitate saline areas and desert. To investigate its strategies involved in salt tolerance, A. halimus was grown hydroponically under controlled conditions with increasing salinity. Plants were harvested and analyzed after 60 days of treatment. The biomass of A. halimus increased by moderate salinity and decreased significantly at high salinity compared to control plants at 400 mM. Despite of the large amounts of Na(+) observed in the leaves of Atriplex plants, leaf water contents and leaf succulence kept on increasing in treated plants and decreased over 150 mM NaCl. This confirmed the compartmentation and the efficient contribution of Na(+) in the osmotic adjustment. Analysis of the metabolic profiles showed an accumulation of carbohydrates and amino acids. The leaf tissues preferentially stored proline, α alanine and sucrose. Increasing NaCl levels were also accompanied by a significant accumulation of malate in leaves. Involvement of these solutes in osmotic adjustment was considered low. Nevertheless, they seemed to have an important role in controlling photosynthesis which capacity was enhanced by low salinity and decreased with increasing salinity (evaluated by actual photochemical efficiency of photosystem II and chlorophyll contents). The unchanged maximum photochemical efficiency of photosystem II accompanied by the increase of the non-photochemical quenching, the enhancement of the total antioxidant activity and the decrease of the malondialdehyde contents in leaves showed efficient protection of membranes and photosystem II from photo-oxidative damage. This protection seemed to be attributed to proline and sucrose largely accumulated in leaves treated with salt. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Impact of Photooxidation and Biodegradation on the Fate of Oil Spilled During the Deepwater Horizon Incident: Advanced Stages of Weathering.

PubMed

Harriman, Brian H; Zito, Phoebe; Podgorski, David C; Tarr, Matthew A; Suflita, Joseph M

2017-07-05

While the biogeochemical forces influencing the weathering of spilled oil have been investigated for decades, the environmental fate and effects of "oxyhydrocarbons" in sand patties deposited on beaches are not well-known. We collected sand patties deposited in the swash zone on Gulf of Mexico beaches following the Deepwater Horizon oil spill. When sand patties were exposed to simulated sunlight, a larger concentration of dissolved organic carbon was leached into seawater than the corresponding dark controls. This result was consistent with the general ease of movement of seawater through the sand patties as shown with a 35 SO 4 2- radiotracer. Ultrahigh-resolution mass spectrometry, as well as optical measurements revealed that the chemical composition of dissolved organic matter (DOM) leached from the sand patties under dark and irradiated conditions were substantially different, but neither had a significant inhibitory influence on the endogenous rate of aerobic or anaerobic microbial respiratory activity. Rather, the dissolved organic photooxidation products stimulated significantly more microbial O 2 consumption (113 ± 4 μM) than either the dark (78 ± 2 μM) controls or the endogenous (38 μM ± 4) forms of DOM. The changes in the DOM quality and quantity were consistent with biodegradation as an explanation for the differences. These results confirm that sand patties undergo a gradual dissolution of DOM in both the dark and in the light, but photooxidation accelerates the production of water-soluble polar organic compounds that are relatively more amenable to aerobic biodegradation. As such, these processes represent previously unrecognized advanced weathering stages that are important in the ultimate transformation of spilled crude oil.

Nrf2 protects photoreceptor cells from photo-oxidative stress induced by blue light.

PubMed

Chen, Wan-Ju; Wu, Caiying; Xu, Zhenhua; Kuse, Yoshiki; Hara, Hideaki; Duh, Elia J

2017-01-01

Oxidative stress plays a key role in age-related macular degeneration and hereditary retinal degenerations. Light damage in rodents has been used extensively to model oxidative stress-induced photoreceptor degeneration, and photo-oxidative injury from blue light is particularly damaging to photoreceptors. The endogenous factors protecting photoreceptors from oxidative stress, including photo-oxidative stress, are continuing to be elucidated. In this study, we evaluated the effect of blue light exposure on photoreceptors and its relationship to Nrf2 using cultured murine photoreceptor (661W) cells. 661W cells were exposed to blue light at 2500 lux. Exposure to blue light for 6-24 h resulted in a significant increase in intracellular reactive oxygen species (ROS) and death of 661W cells in a time-dependent fashion. Blue light exposure resulted in activation of Nrf2, as indicated by an increase in nuclear translocation of Nrf2. This was associated with a significant induction of expression of Nrf2 as well as an array of Nrf2 target genes, including antioxidant genes, as indicated by quantitative reverse transcription PCR (qRT-PCR). In order to determine the functional role of Nrf2, siRNA-mediated knockdown studies were performed. Nrf2-knockdown in 661W cells resulted in significant exacerbation of blue light-induced reactive oxygen species levels as well as cell death. Taken together, these findings indicate that Nrf2 is an important endogenous protective factor against oxidative stress in photoreceptor cells. This suggests that drugs targeting Nrf2 could be considered as a neuroprotective strategy for photoreceptors in AMD and other retinal conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of photooxidation on membrane integrity in Salix nigra seeds

PubMed Central

Roqueiro, Gonzalo; Facorro, Graciela B.; Huarte, Mónica G.; Rubín de Celis, Emilio; García, Fernando; Maldonado, Sara; Maroder, Horacio

2010-01-01

Background and Aims Salix nigra seeds are desiccation-tolerant, as are orthodox seeds, although in contrast to other orthodox seeds they lose viability in a few weeks at room temperature. They also differ in that the chloroplasts of the embryo tissues conserve their chlorophyll and endomembranes. The aim of this paper was to investigate the role of chlorophyll in seed deterioration. Methods Seeds were aged at different light intensities and atmospheric conditions. Mean germination time and normal and total germination were evaluated. The formation of free radicals was assessed using electronic spin resonance spectroscopy, and changes in the fatty acid composition from phospholipids, galactolipids and triglycerides using gas–liquid chromatography. Membrane integrity was studied with electronic spin resonance spin probe techniques, electrolyte leakage and transmission electron microscopy. Key Results Light and oxygen played an important role in free-radical generation, causing a decrease in normal germination and an increase in mean germination time. Both indices were associated with a decrease in polyunsaturated fatty acids derived from membrane lipids as phospholipids and galactolipids. The detection of damage in thylakoid membranes and an increase in plasmalemma permeability were consistent with the decrease in both types of lipids. Triglycerides remained unchanged. Light-induced damage began in outermost tissues and spread inwards, decreasing normal germination. Conclusions Salix nigra seeds were very susceptible to photooxidation. The thylakoid membranes appeared to be the first target of the photooxidative process since there were large decreases in galactolipids and both these lipids and the activated chlorophyll are contiguous in the structure of that membrane. Changes in normal germination and mean germination time could be explained by the deteriorative effects of oxidation. PMID:20338949

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes

NASA Astrophysics Data System (ADS)

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-06-01

This study deals with the exploration of NixCo1-xFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co0.4Ni0.6Fe2O4 (154.02 m2 g-1). Co0.4Ni0.6Fe2O4 showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe2O4 was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH4 on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni2+ in to the cobalt ferrite lattice due to octahedral site preference of Ni2+. Almost 99% degradation was achieved in 20 min using NiFe2O4 nanoparticles as catalyst.

Highly sensitive fluorescence detection of metastatic lymph nodes of gastric cancer with photo-oxidation of protoporphyrin IX.

PubMed

Koizumi, N; Harada, Y; Beika, M; Minamikawa, T; Yamaoka, Y; Dai, P; Murayama, Y; Yanagisawa, A; Otsuji, E; Tanaka, H; Takamatsu, T

2016-08-01

The establishment of a precise and rapid method to detect metastatic lymph nodes (LNs) is essential to perform less invasive surgery with reduced gastrectomy along with reduced lymph node dissection. We herein describe a novel imaging strategy to detect 5-aminolevulinic acid (5-ALA)-induced protoporphyrin IX (PpIX) fluorescence in excised LNs specifically with reduced effects of tissue autofluorescence based on photo-oxidation of PpIX. We applied the method in a clinical setting, and evaluated its feasibility. To reduce the unfavorable effect of autofluorescence, we focused on photo-oxidation of PpIX: Following light irradiation, PpIX changes into another substance, photo-protoporphyrin, via an oxidative process, which has a different spectral peak, at 675 nm, whereas PpIX has its spectral peak at 635 nm. Based on the unique spectral alteration, fluorescence spectral imaging before and after light irradiation and subsequent originally-developed image processing was performed. Following in vitro study, we applied this method to a total of 662 excised LNs obtained from 30 gastric cancer patients administered 5-ALA preoperatively. Specific visualization of PpIX was achieved in in vitro study. The method allowed highly sensitive detection of metastatic LNs, with sensitivity of 91.9% and specificity of 90.8% in the in vivo clinical trial. Receiver operating characteristic analysis indicated high diagnostic accuracy, with the area under the curve of 0.926. We established a highly sensitive and specific 5-ALA-induced fluorescence imaging method applicable in clinical settings. The novel method has a potential to become a useful tool for intraoperative rapid diagnosis of LN metastasis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Plasma Rich in Growth Factors Enhances Wound Healing and Protects from Photo-oxidative Stress in Dermal Fibroblasts and 3D Skin Models.

PubMed

Anitua, Eduardo; Pino, Ander; Jaen, Pedro; Orive, Gorka

2016-01-01

Optimal skin repair has been a desired goal for many researchers. Recently, plasma rich in growth factors (PRGF) has gained importance in dermatology proving it is beneficial effects in wound healing and cutaneous regeneration. The anti-fibrotic, pro-contractile and photo-protective effect of PRGF on dermal fibroblasts and 3D skin models has been evaluated. The effect against TGFβ1 induced myofibroblast differentiation was tested. Cell contractile activity over collagen gel matrices was analyzed and the effect against UV derived photo-oxidative stress was assessed. The effectiveness of PRGF obtained from young aged and middle aged donors was compared. Furthermore, 3D organotypic skin explants were used as human skin models with the aim of analyzing ex vivo cutaneous preventive and regenerative photo-protection after UV exposure. TGFβ1 induced myofibroblast levels decreased significantly after treatment with PRGF while the contractile activity increased compared to the control group. After UV irradiation, cell survival was promoted while apoptotic and ROS levels were noticeably reduced. Photo-exposed 3D explants showed higher levels of metabolic activity and lower levels of necrosis, cell damage, irritation and ROS formation when treated with PRGF. The histological integrity and connective tissue fibers showed lower signals of photodamage among PRGF injected skin models. No significant differences for the assessed biological outcomes were observed when PRGF obtained from young aged and middle aged donors were compared. These findings suggest that this autologous approach might be useful for antifibrotic wound healing and provide an effective protection against sun derived photo-oxidative stress regardless the age of the patient.

Effects of NOx on the molecular composition of secondary organic aerosol formed by the ozonolysis and photooxidation of α-pinene

NASA Astrophysics Data System (ADS)

Park, Jun-Hyun; Babar, Zaeem Bin; Baek, Sun Jong; Kim, Hyun Sik; Lim, Ho-Jin

2017-10-01

The molecular composition of secondary organic aerosol (SOA), obtained from the ozonolysis and photooxidation of α-pinene, was investigated using ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) in negative ion mode electrospray ionization (ESI). SOA formation was performed in an indoor smog chamber. The molecular formulae of individual species were identified on the basis of the measured ionic mass using guidelines, such as number of atoms, elemental ratios, and the nitrogen rule. In each of the SOAs obtained, 815-3501 monomeric and oligomeric (mainly dimeric) species were identified below m/z 800. From ozonolysis, mainly 95% of the typical oxygenated species (CHO) were detected, whereas from photooxidation under high NOx conditions, 32% of nitrogen-containing species (CHON) were detected. Several common intense species (e.g., C9H14O6, C10H14O6, C10H16O5, C17H26O7, C19H28O9, C10H15NO8, and C10H15NO9) could be listed as candidate tracers for the conventional tracers for α-pinene SOA. The increased percentage of CHON as a primary effect of NOx on the SOA composition evidently affected other physicochemical parameters, such as elemental ratios (i.e., O/C, H/C, and N/C), the double-bond equivalent (DBE), the carbon oxidation state (OSC), and the organic-mass-to-carbon ratio (OM/OC). The O/C and OM/OC for CHON were greater than those observed for CHO, indicating that nitrogen preferentially exists in the oxidized form (e.g., -ONO2). The complexity of oligomerization was observed in DBE and OM/OC according to the number of carbon atoms.

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Complexes of lutein with bovine and caprine caseins and their impact on lutein chemical stability in emulsion systems: Effect of arabinogalactan.

PubMed

Mora-Gutierrez, A; Attaie, R; Núñez de González, M T; Jung, Y; Woldesenbet, S; Marquez, S A

2018-01-01

Lutein is an important xanthophyll carotenoid with many benefits to human health. Factors affecting the application of lutein as a functional ingredient in low-fat dairy-like beverages (pH 6.0-7.0) are not well understood. The interactions of bovine and caprine caseins with hydrophobic lutein were studied using UV/visible spectroscopy as well as fluorescence. Our studies confirmed that the aqueous solubility of lutein is improved after binding with bovine and caprine caseins. The rates of lutein solubilization by the binding to bovine and caprine caseins were as follows: caprine α S1 -II-casein 34%, caprine α S1 -I-casein 10%, and bovine casein 7% at 100 μM lutein. Fluorescence of the protein was quenched on binding supporting complex formation. The fluorescence experiments showed that the binding involves tryptophan residues and some nonspecific interactions. Scatchard plots of lutein binding to the caseins demonstrated competitive binding between the caseins and their sites of interaction with lutein. Competition experiments suggest that caprine α S1 -II casein will bind a larger number of lutein molecules with higher affinity than other caseins. The chemical stability of lutein was largely dependent on casein type and significant increases occurred in the chemical stability of lutein with the following pattern: caprine α S1 -II-casein > caprine α S1 -I-casein > bovine casein. Addition of arabinogalactan to lutein-enriched emulsions increases the chemical stability of lutein-casein complexes during storage under accelerated photo-oxidation conditions at 25°C. Therefore, caprine α S1 -II-casein alone and in combination with arabinogalactan can have important applications in the beverage industry as carrier of this xanthophyll carotenoid (lutein). Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

PHOTOCATALYTIC OXIDATION OF METHYL-TERT-BUTYL ETHER FOR DRINKING WATER TREATMENT

EPA Science Inventory

The photo-oxidation of methyl tert-butyl ether (MTBE) in water was investigated to determine the feasibility of using photocatalysis for the treatment of MTBE-contaminated drinking water. The feasibility assessment was conducted using slurries of titanium dioxide in both a photo-...

PHOTOOXIDATION OF HYDROCARBONS TO PARTIAL OXYGENATES IN AN AQUEOUS ENVIRONMENT [EXHIBIT, POSTER

EPA Science Inventory

The USEPA is researching the use of alternative oxidation technologies (AOT's) as a catalytic process for the selective oxidation of hydrocarbon substrates. One AOT currently under investigation is the use of photocatalysis employed with a laminar thin-film falling reactor. Thi...

EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

EPA Science Inventory

Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of α-pinene and isop...

Photo-oxidation of ergosterol: indirect detection of antioxidants photosensitizers or quenchers of singlet oxygen.

PubMed

Lagunes, Irene; Trigos, Ángel

2015-04-01

Consumption of antioxidant supplements is associated to prevention of several diseases. However, recent studies suggest that antioxidants, besides scavenge free radicals could lead development of tumors. Due to conflicting reports on the antioxidant benefits, the capacity to photosensitize the generation of singlet oxygen of seven natural antioxidants was evaluated through photo-oxidation of ergosterol which proved to be an efficient method of indirect detection of singlet oxygen. Our results showed that curcumin, resveratrol and quercetin have pro-oxidant activity due they act as photosensitizers in generation of singlet oxygen. In addition, we observed that genistein, naringenin, β-carotene and gallic acid besides their antioxidant activity against ROS radicals, are capable of quenching ROS non-radicals as singlet oxygen. Finally, our results allow us to propose a new approach in classification of natural antioxidants scavengers of free radicals, based on their activity as quenchers of singlet oxygen or as photosensitizers in singlet oxygen generation. Copyright © 2015. Published by Elsevier B.V.

Observations of liquid-liquid phase separation in several types of secondary organic materials free of inorganic salts

NASA Astrophysics Data System (ADS)

Song, M.; Liu, P.; Martin, S. T.; Bertram, A. K.; Ham, S.

2016-12-01

Particles consisting of secondary organic materials (SOMs) are ubiquitous in the atmosphere. In order to predict the role of these particles in climate, visibility, and atmospheric chemistry, knowledge of the phase states of the particles is required. However, the phase states of the SOMs are still poorly understood. Herein we focused on liquid-liquid phase separation in different types of SOM particles free of inorganic salts produced by the ozonolysis of β-caryophyllene, ozonolysis of limonene, photo-oxidation of isoprene, and photo-oxidation of toluene. Liquid-liquid phase separation was investigated using optical microscopy and SOM particle mass concentrations ranging from 15 µg·m-3 to 7000 µg·m-3. During humidity cycles, liquid-liquid phase separation was observed in β-caryophyllene-derived SOM and limonene-derived SOM particles while no liquid-liquid phase separation was observed in isoprene-derived SOM and toluene-derived SOM particles. Results from the studies will be presented.

[Photosensitization and photoprotection by some drugs, metabolites and other compounds].

PubMed

Lozovskaia, E L; Makareeva, E N; Makedonov, I U

1997-01-01

Photosensitizing and photoprotecting efficiency of about a hundred of compounds, mainly drugs, was studied. The method based on chemiluminescence occurred along with photooxidation of glycyltryptophan under irradiation in UVB range in solution was used for testing. As a measure of photosensitizing efficiency the concentration of photosensitizer which induced two-fold increase of chemiluminescence intensity was chosen. The most effective photosensitizers are riboflavin, FAD, furagin, psoralene, vicasol, benzobarbital, mydocalm, angelicyn, furadonin, ethacridin, diazolin, folic acid. With regard to pharmacological doses of drugs in organism more dangerous sensitizers (in descending order) are p-aminosalicylic acid, furagin, riboflavin, benzobarbital, thiopental, chloramphenicol, nicodin, mydocalm, furadonin, oxolonic acid, furazolidone, psoralene, nicotinamide and diazolin. Photoprotecting effect was described by the concentration at which chemiluminescence intensity decreased twice. The most effective photoprotectors are etamsilat, quercetin, ftivazid, chlorpromazine, diprazine, thioridazine, aminophenazone, oxaphenamide. Concentration dependence for some of these drugs (etamsilat, chlorpromazine, diprazine, thioridazine) is non-monotonous: they inhibit photooxidation in low concentration (about 10(-7)-10(-6) M), but at higher concentrations (10(-5)-10(-4) M) photosensitization dominates over photoprotection.

Characterization of a photoproduct of 7,12-dimethylbenz[alpha]anthracene and its effects on chick-embryo cells in culture.

PubMed Central

Warshawsky, D; Kerns, E; Bissell, M J; Calvin, M

1977-01-01

A common impurity of 7,12-dimethylbenz[alpha]anthracene was more effective than 7,12-dimethylbenz[alpha]anthracene in inducing morphological alterations, and in causing an increase in glucose uptake, DNA synthesis and cell number in chick-embryo fibroblasts. Gradual morphological transformation follows the increase in DNA synthesis after 2 days when either primary or secondary cultures are treated with 3 microgram of the compound/ml. The compound, isolated from 7,12-dimethylbenz[alpha]anthracene by alumina column chromatography, was characterized by t.l.c., mass spectroscopy, carbon-hydrogen analysis, u.v. and nuclear-magnetic-resonance spectroscopy and thermal decomposition. It was the photo-oxidation product of 7,12-dimethylbenz[alpha]anthracene, 7,12-epidioxy-7,12-dimethylbenz[alpha]anthracene. It is suggested that some of the biological effects observed after treatment of cultures with 7,12-dimethylbenz[alpha]anthracene may be due in part to the presence of the photo-oxidation product. PMID:407902

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Fourier transform infrared analysis of aerosol formed in the photooxidation of 1-octene

NASA Astrophysics Data System (ADS)

Palen, Edward J.; Allen, David T.; Pandis, Spyros N.; Paulson, Suzanne; Seinfeld, John H.; Flagan, Richard C.

The chemical composition of aerosol generated in the photooxidation of 1-octene was examined using infrared microscopy interfaced with a low pressure impactor. The low pressure impactor segregated the aerosol into eight size fractions and deposited the aerosol onto ZnSe impaction substrates. The ZnSe surfaces were transparent in the mid-infrared region and therefore allowed direct analysis of the aerosol, with no extraction, using infrared microscopy. Infrared spectra of the size segregated aerosol showed strong absorbances due to ketone, alcohol, carboxylic acid and organonitrate functional groups. Absorbance features were relatively independent of particle size, with the exception of the carboxylic acid absorbances, which were found only in the largest aerosol size fractions. Molar loadings for each of the groups were estimated, based on model compound calibration standards. The molar loadings indicate that most aerosol species are multifunctional, with an average of one ketone group per molecule, an alcohol group in two of every three molecules and an organonitrate group in one of every three molecules.

Effect of ultraviolet radiation in the photo-oxidation of High Density Polyethylene and Biodegradable Polyethylene films

NASA Astrophysics Data System (ADS)

Martínez-Romo, A.; González Mota, R.; Bernal, J. J. Soto; Frausto Reyes, C.; Rosales Candelas, I.

2015-01-01

One of the most widely used plastics in the world is the High density polyethylene (HDPE), it is a stable material due to its carbon-carbon bonds, causing their slow degradation; which is why we are looking for alternative ways to accelerate the degradation process of this polymer. An alternative is the addition of oxidized groups in its molecular structure, which results in the development of polymers susceptible to biodegradation (PE-BIO). In this paper, HDPE and PE-BIO films were exposed to UV-B radiation (320-280 nm) at different exposure times, 0-60 days. The effects of UV radiation in samples of HDPE and PE-BIO were characterized using infrared spectroscopy with attenuated total reflectance (ATR). The results show that the exposed materials undergo changes in their molecular structure, due to the infrared bands formed which corresponds to the photo-oxidation of HDPE and PE films when submitted to UV-B radiation.

Short-term effects of military fog oil on the fountain darter (Etheostoma fonticola).

PubMed

Ryan, T A; Kohl, A N; Soucek, D J; Smith, T S; Brandt, T M; Bonner, T H; Cropek, D M

2013-11-01

Toxicity tests evaluated chronic and sublethal effects of fog oil (FO) on a freshwater endangered fish. FO is released during military training as an obscurant smoke that can drift into aquatic habitats. Fountain darters, Etheostoma fonticola, of four distinct life stages were exposed under laboratory conditions to three forms of FO. FO was vaporized into smoke and allowed to settle onto water, violently agitated with water, and dosed onto water followed by photo-oxidization by ultraviolet irradiation. Single smoke exposures of spawning adult fish did not affect egg production, egg viability, or adult fish survival in 21-day tests. Multiple daily smoke exposures induced mortality after 5 days for larvae fish. Larvae and juvenile fish were more sensitive than eggs in 96-h lethal concentration (LC50) tests with FO–water mixtures and photo-oxidized FO. Water-soluble FO components photo-modified by ultraviolet radiation were the most toxic, thus indicating the value of examining weathering and aging of chemicals for the best determination of environmental impact.

On the front and back side quantum efficiency differences in semi-transparent organic solar cells and photodiodes

NASA Astrophysics Data System (ADS)

Bouthinon, B.; Clerc, R.; Verilhac, J. M.; Racine, B.; De Girolamo, J.; Jacob, S.; Lienhard, P.; Joimel, J.; Dhez, O.; Revaux, A.

2018-03-01

The External Quantum Efficiency (EQE) of semi-transparent Bulk Hetero-Junction (BHJ) organic photodiodes processed in air shows significant differences when measured from the front or back side contacts. This difference was found significantly reduced when decreasing the active layer thickness or by applying a negative bias. This work brings new elements to help understanding this effect, providing a large set of experiments featuring different applied voltages, active layers, process conditions, and electron and hole layers. By means of detailed electrical simulations, all these measurements have been found consistent with the mechanisms of irreversible photo-oxidation, modeled as deep trap states (and not as p-type doping). The EQE measurement from front and back sides is thus a simple and efficient way of monitoring the presence and amplitude of oxygen contamination in BHJ organic solar cells and photodiodes.

Amino acid sequence of tyrosinase from Neurospora crassa.

PubMed Central

Lerch, K

1978-01-01

The amino-acid sequence of tyrosinase from Neurospora crassa (monophenol,dihydroxyphenylalanine:oxygen oxidoreductase, EC 1.14.18.1) is reported. This copper-containing oxidase consists of a single polypeptide chain of 407 amino acids. The primary structure was determined by automated and manual sequence analysis on fragments produced by cleavage with cyanogen bromide and on peptides obtained by digestion with trypsin, pepsin, thermolysin, or chymotrypsin. The amino terminus of the protein is acetylated and the single cysteinyl residue 96 is covalently linked via a thioether bridge to histidyl residue 94. The formation and the possible role of this unusual structure in Neurospora tyrosinase is discussed. Dye-sensitized photooxidation of apotyrosinase and active-site-directed inactivation of the native enzyme indicate the possible involvement of histidyl residues 188, 192, 289, and 305 or 306 as ligands to the active-site copper as well as in the catalytic mechanism of this monooxygenase. PMID:151279

Photooxidation of carbofuran by a polychromatic UV irradiation without and with hydrogen peroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benitez, F.J.; Beltran-Heredia, J.; Gonzalez, T.

The photodegradation of carbofuran aqueous solutions has been conducted with direct photolysis provided by a polychromatic UV radiation source and by the combination of this UV radiation with hydrogen peroxide. In both processes, the decomposition level obtained as a function of the operating variables is reported, and the presence of tert-butyl alcohol, a scavenger of free radicals, is discussed. While the contribution of hydroxyl radicals is negligible in the direct photolysis, its reactions in the UV/H{sub 2}O{sub 2} system clearly increase the carbofuran decomposition and therefore must be taken into account in the reaction rate equation for the total degradation.more » From the mechanisms proposed, the quantum yields for the direct photolysis and the kinetic constants for the reaction between carbofuran and the hydroxyl radicals generated in the H{sub 2}O{sub 2} photolysis in the combined process are respectively evaluated.« less

Diatom aggregation and dimethylsulfide production in phytoplankton blooms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crocker, K.M.

1994-01-01

Phytoplankton blooms are crucial links in many of the earth's biogeochemical cycles. Blooms take up atmospheric carbon through photosynthesis, and sequester it on the ocean floor by sinking. Aggregation of single cells into [open quote]marine snow[close quote] particles speeds up the sinking of algal cells. Laboratory studies investigating the process of aggregation show that some species have a higher probability of aggregating than others, and that there exist several mechanisms for causing aggregation. Field studies confirm that some species are more likely to be found in aggregates than in the surrounding seawater. High latitude Premnesiophyte blooms are found to producemore » large amounts of dimethylsulflde (DMS), believed to be an important chemical in global thermoregulation. DMS is found to vary diurnally, possibly due to photooxidation by ultraviolet light. This possibility links the effects of DMS on cloud formation with the effects of increased ultraviolet light penetrating the earths ozone layer.« less

[Study on transformation mechanism of SOA from biogenic VOC under UV-B condition].

PubMed

Li, Ying-Ying; Li, Xiang; Chen, Jian-Min

2011-12-01

A laboratory study was carried out to investigate the biogenic volatile organic compounds (BVOC) in a lab-made glass chamber. The secondary organic aerosol (SOA) products can be detected under the UV photooxidation of BVOC. Pelargonium x Citrenella was chosen as the target plant in this research because it can release a large amount of BVOCs. The predominant 7 alkene and ketol compounds were detected by using solid phase microextraction (SPME) sampling and gas chromatography/mass spectrometry (GC/MS) analysis. The photochemical experiment indicated that these BVOC can be rapidly oxidized into SOA under UV-B irradiation. A tandem differential mobility analyzer (TDMA) was used to measure the size distribution and the hygroscopicity of the SOA. The particle diameter was in the range of 50 nm to 320 nm. The high hygroscopicity of SOA was also obtained and the size increased from 1.05 to 1.11 during the wet experiment.

Optical and mechanical properties of UV-weathered biodegradable PHBV/PBAT nanocomposite films containing halloysite nanotubes

NASA Astrophysics Data System (ADS)

Scarfato, P.; Avallone, E.; Acierno, D.; Russo, P.

2014-05-01

Recently, the increasing use of plastics, stringent environmental issues and the awareness of the progressive reduction of available petrochemical resources have ever more guided the research interest towards the investigation and development of innovative materials intrinsically biodegradable or derived from renewable sources, and generally known as bio-based polymers. Amongst the biobased and biodegradable polymers, many investigations were reported in literature about a family of polyesters known as poly(hydroxyalkanoate)s (PHAs), one of whose most prevalent is poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In this context, here we report the results of a photo-degradation study performed on biodegradable blown film samples based on a commercial grade PHBV/PBAT formulation. The films, subjected to photo-oxidative weathering in a climatic chamber under UV exposure, were systematically analysed in order to check the chemico-physical changes induced by the aging protocol, taking the as-produced films as the reference materials.

Oxidization of squalene, a human skin lipid: a new and reliable marker of environmental pollution studies.

PubMed

Pham, D-M; Boussouira, B; Moyal, D; Nguyen, Q L

2015-08-01

A review of the oxidization of squalene, a specific human compound produced by the sebaceous gland, is proposed. Such chemical transformation induces important consequences at various levels. Squalene by-products, mostly under peroxidized forms, lead to comedogenesis, contribute to the development of inflammatory acne and possibly modify the skin relief (wrinkling). Experimental conditions of oxidation and/or photo-oxidation mechanisms are exposed, suggesting that they could possibly be bio-markers of atmospheric pollution upon skin. Ozone, long UVA rays, cigarette smoke… are shown powerful oxidizing agents of squalene. Some in vitro, ex vivo and in vivo testings are proposed as examples, aiming at studying ingredients or products capable of boosting or counteracting such chemical changes that, globally, bring adverse effects to various cutaneous compartments. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

PubMed

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Secondary organic aerosol formation from isoprene photo-oxidation during cloud condensation-evaporation cycles (CUMULUS project)

NASA Astrophysics Data System (ADS)

Brégonzio-Rozier, Lola; Siekmann, Frank; Giorio, Chiara; Temime-Roussel, Brice; Pangui, Edouard; Morales, Sébastien; Gratien, Aline; Ravier, Sylvain; Monod, Anne; Doussin, Jean-Francois

2014-05-01

It is acknowledged that atmospheric photo-oxidation of Volatile Organic Compounds (VOC) leads to the formation of less volatile oxidized species. These compounds can undergo gas-to-particle conversion, leading to the formation of Secondary Organic Aerosols (SOA) in the atmosphere. Nevertheless, some of these oxidized species are water soluble and could also partition into cloud droplets. Higher molecular weight and less volatile compounds could be produced in the aqueous phase and remain in the particle phase after water evaporation (Ervens et al., 2011). The aim of the present work is to study SOA formation in the presence of cloud droplets during isoprene photo-oxidation. To this end, an original multiphase approach in a simulation chamber was set up in order to investigate the chemistry occurring in the gaseous, particulate and aqueous phases, and the exchange between these phases. Experiments were performed, within the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere), in the CESAM chamber (Wang et al., 2011). This chamber was designed to investigate multiphase processes under realistic actinic flux, and accurate control of both temperature and relative humidity. A specific protocol was set up to produce cloud events in the simulation chamber exhibiting a significant lifetime in the presence of light (10-12 minutes). By using this protocol, many clouds could be generated in a single experiment. In each experiment, around 800 ppb of isoprene was injected in the chamber together with HONO under dry conditions before irradiation. A Fourier Transform Infrared Spectrometer (FTIR), a Proton Transfer Reaction Mass Spectrometer (PTR-TOF-MS) and NOx and O3 analyzers were used to analyze gas-phase composition. Dried SOA size distributions and total concentrations were measured by a Scanning Mobility Particle Sizer (SMPS). An Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS) was also used to investigate aerosol composition. Cloud droplets size distributions were measured by a white light Optical Particle Counter (OPC). In all experiments, the dissolution of gaseous oxidation products into aqueous phase and SOA production have been observed during isoprene photo-oxidation in the presence of a cloud event. The overall results in additional SOA mass production and the dynamic of gaseous oxidation products and SOA mass concentrations will be presented. Ervens, B. et al. (2011). Atmospheric Chemistry and Physics 11(21): 11069-11102. Wang, J. et al. (2011). Atmospheric Measurement Techniques 4(11): 2465-2494.

Chemical Modifications that Affect Nutritional and Functional Properties of Proteins.

ERIC Educational Resources Information Center

Richardson, T.; Kester, J. J.

1984-01-01

Discusses chemical alterations of selected amino acids resulting from environmental effects (photooxidations, pH extremes, thermally induced effects). Also dicusses use of intentional chemical derivatizations of various functional groups in amino acid residue side chains and how recombinant DNA techniques might be useful in structure/function…

Modelling of polymer photodegradation for solar cell modules

NASA Technical Reports Server (NTRS)

Guillet, J. E.

1982-01-01

A computer program which simulates the complex processes of photooxidation which take place in a polymer upon prolonged exposure outdoors causing it to fail in photovoltaic and other applications. The method calculates from an input data set of elementary reactions and rates the concentration profiles of all species over time.

The response of Asterochloris erici (Ahmadjian) Skaloud et Peksa to desiccation: a proteomic approach

USDA-ARS?s Scientific Manuscript database

The study of desiccation tolerance of lichens, and of their photobionts in particular, has frequently focused on the antioxidant system that protects the cell against photo-oxidative stress during dehydration/rehydration cycles. Thus, in this work we carried out proteomic and transcript analyses of ...

A Simple Photochemical Experiment for the Advanced Laboratory.

ERIC Educational Resources Information Center

Rosenfeld, Stuart M.

1986-01-01

Describes an experiment to provide students with: (1) an introduction to photochemical techniques and theory; (2) an experience with semimicro techniques; (3) an application of carbon-14 nuclear magnetic resonance; and (4) a laboratory with some qualities of a genuine experiment. These criteria are met in the photooxidation of 9,…

EMERGING TECHNOLOGY REPORT: DESTRUCTION OF ORGANIC CONTAMINANTS IN AIR USING ADVANCED ULTRAVIOLET FLASHLAMPS

EPA Science Inventory

This paper describes a new process for photo-oxidation of volatile organic compounds (VOCs) in air using an advanced ultraviolet source, a Purus xenon flashlamp. The flashlamps have greater output at 200-250 nm than medium-pressure mercury lamps at the same power and therefore ca...

Surviving metabolic arrest: photosynthesis during desiccation and rehydration in resurrection plants.

PubMed

Challabathula, Dinakar; Puthur, Jos T; Bartels, Dorothea

2016-02-01

Photosynthesis is the key process that is affected by dehydration in plants. Desiccation-tolerant resurrection plants can survive conditions of very low relative water content. During desiccation, photosynthesis is not operational, but is recovered within a short period after rehydration. While homoiochlorophyllous resurrection plants retain their photosynthetic apparatus during desiccation, poikilochlorophyllous resurrection species dismantle chloroplasts and degrade chlorophyll but resynthesize them again during rehydration. Dismantling the chloroplasts avoids the photooxidative stress in poikilochlorophyllous resurrection plants, whereas it is minimized in homoiochlorophyllous plants through the synthesis of antioxidant enzymes and protective proteins or metabolites. Although the cellular protection mechanisms in both of these species vary, these mechanisms protect cells from desiccation-induced damage and restore photosynthesis upon rehydration. Several of the proteins synthesized during dehydration are localized in chloroplasts and are believed to play major roles in the protection of photosynthetic structures and in recovery in resurrection species. This review focuses on the strategies of resurrection plants in terms of how they protect their photosynthetic apparatus from oxidative stress during desiccation without membrane damage and with full recovery during rehydration. We review the role of the dehydration-induced protection mechanisms in chloroplasts and how photosynthesis is restored during rehydration. © 2015 New York Academy of Sciences.

Identification of keto- and hydroxy-dicarboxylic acids in remote marine aerosols from the western North Pacific: GC and GC/TOF-MS measurements

NASA Astrophysics Data System (ADS)

Vani, D.; Kawamura, K.; Tachibana, E.; Boreddy, S. K. R.

2015-12-01

Dicarboxylic acids (diacids) are dominant components of organic aerosols in the atmosphere. They contribute significantly to the total aerosol mass and have a serious impacts on global climate changes. However, studies on keto- and hydroxy-diacids in marine aerosols are limited. Compare to diacids, keto- and hydroxy-diacids are more hygroscopic due to the additional polar groups (OH and CO) and, hence, acts as cloud condensation nuclei (CCN). Molecular characterization of these compounds provides insight into organic aerosols sources and transformation pathways. We collected marine aerosols from remote Chichijima Island in the western North Pacific from December 2010 to November 2011 and studied for water-soluble keto- and hydroxy-diacids. Carboxyl groups were derivatized to dibutyl esters with 14% boron trifluoride/n-butanol, whereas hydroxyl groups were derivatized to trimethylsilyl ethers using N,O-Bis (trimethylsilyl) trifluoroacetamide (BSTFA). After two-step derivatization, samples were injected to GC, GC/MS and GC/TOF-MS. In the GC chromatogram, we detected several new peaks after BSTFA derivatization of dibutyl ester fraction. Based on mass spectral interpretation, we found these peaks as homologues series of hydroxy-diacids and keto-diacids. Some of these hydroxy-diacids have been individually reported in literature in the laboratory photo-oxidation experiments and forest environments samples. But, there are no evidences to prove their sources and formation mechanism in the atmosphere. Here, we report for the first time homologous series of hydroxy-diacids (hC3di-hC6di) and keto-diacid (oxaloacetic acid, enol and keto forms) in remote marine atmosphere. Molecular distributions of hydroxy-diacids generally showed the predominance of malic acid followed by tartronic acid. Both hydroxy- and keto-diacids show significant positive correlation with oxalic acid and SO42-, suggesting that they are generated in the atmosphere and play an important role in the formation of smaller diacids through aqueous phase photo-oxidation.

Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

NASA Astrophysics Data System (ADS)

Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

2013-11-01

In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292-295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.

Photo-Initiated Electron Transfer Within the P. denitrificans Cytochrome bc1 Complex: The mobility of the Iron Sulfur Protein is modulated by the occupant of the Qo site†

PubMed Central

Havens, Jeffrey; Castellani, Michela; Kleinschroth, Thomas; Ludwig, Bernd; Durham, Bill; Millett, Francis

2011-01-01

Domain rotation of the Rieske iron-sulfur protein (ISP) between the cytochrome (cyt) b and cyt c1 redox centers plays a key role in the mechanism of the cyt bc1 complex. Electron transfer within the cyt bc1 complex of P. denitrificans was studied using a ruthenium dimer to rapidly photo-oxidize cyt c1 within 1 μs and initiate the reaction. In the absence of any added quinol or inhibitor of the bc1 complex at pH 8.0, electron transfer from reduced ISP to cyt c1 was biphasic with rate constants of k1f = 6300 ± 3000 s−1 and k1s = 640 ± 300 s−1 and amplitudes of 10 ± 3% and 16 ± 4 % of the total amount of cyt c1 photooxidized. Upon addition of any of the Pm type inhibitors MOA-stilbene, myxothiazol, or azoxystrobin to cyt bc1 in the absence of quinol, the total amplitude increased 2-fold, consistent with a decrease in redox potential of the ISP. In addition, the relative amplitude of the fast phase increased significantly, consistent with a change in the dynamics of the ISP domain rotation. In contrast, addition of the Pf type inhibitors JG-144 and famoxadone decreased the rate constant k1f by 5 to 10-fold, and increased the amplitude over 2-fold. Addition of quinol substrate in the absence of inhibitors led to a two-fold increase in the amplitude of the k1f phase. The effect of QH2 on the kinetics of electron transfer from reduced ISP to cyt c1 was thus similar to that of the Pm inhibitors and very different from that of the Pf inhibitors. The current results indicate that the species occupying the Qo site has a significant conformational influence on the dynamics of the ISP domain rotation. PMID:22026826

The photodegradation of cadmium yellow paints in Henri Matisse's Le Bonheur de vivre (1905-1906)

NASA Astrophysics Data System (ADS)

Mass, Jennifer L.; Opila, Robert; Buckley, Barbara; Cotte, Marine; Church, Jonathan; Mehta, Apurva

2013-04-01

Evidence for the alteration of the yellow paints in Henri Matisse's Le Bonheur de vivre (1905-1906, The Barnes Foundation) has been observed since the 1990s. The changes in this iconic work of Matisse's Fauvist period include lightening, darkening, and flaking of the yellow paints. Handheld X-ray fluorescence (XRF) and multispectral imaging surveys reveal that the degradation is confined to cadmium yellow (CdS) paints. The discoloration of cadmium yellow paints in Impressionist, Post-Impressionist and early modernist work from the 1880s through the 1920s has been ascribed to the photo-oxidative degradation of CdS. Preliminary investigations of the degraded yellow paints in this work involved Cd LIII-edge X-ray Absorption Near Edge Spectroscopy (XANES) at the Stanford Synchrotron Radiation Light Source (SSRL Menlo Park, California) and Scanning Electron Microscopy-energy dispersive X-ray analysis (SEM-EDS) at the Winterthur Museum Scientific Research and Analysis Laboratory. To determine if the visual changes in the paints did in fact indicate photo-oxidative degradation and if different chemistries could be observed for the lightened versus darkened regions, synchrotron radiation-micro Fourier Transform InfraRed (SR-μFTIR) spectroscopy, X-ray Fluorescence (SR-μXRF) mapping and micro X-ray Absorption Near Edge Spectroscopy (μXANES) mapping at the Cd LIII-edge of the altered paint cross-sections were carried out at the European synchrotron radiation facility (ESRF, Grenoble, France) beamline ID-21. The goal is to elucidate the discoloration mechanisms observed in the paint using elemental and speciation mapping. The μXANES mapping and SR-FTIR imaging showed a substantial enrichment of CdCO3 in the off-white surface crust of the faded/discolored CdS paint. This suggests that the CdCO3 is present as an insoluble photodegradation product rather than solely a paint filler or starting reagent. Additionally, oxalates and sulfates were found to be concentrated at the alteration surface.

In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

PubMed

Poulain, Laurent; Katrib, Yasmine; Isikli, Estelle; Liu, Yao; Wortham, Henri; Mirabel, Philippe; Le Calvé, Stéphane; Monod, Anne

2010-09-01

Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Real refractive indices and formation yields of secondary organic aerosol generated from photooxidation of limonene and α-pinene: the effect of the HC/NO(x) ratio.

PubMed

Kim, Hwajin; Barkey, Brian; Paulson, Suzanne E

2012-06-21

The refractive index is an important property affecting aerosol optical properties, which in turn help determine the aerosol direct effect and satellite retrieval results. Here, we investigate the real refractive indices (m(r)) of secondary organic aerosols (SOA) generated from the photooxidation of limonene and α-pinene with different HC/NO(x) ratios. Refractive indices were obtained from polar nephelometer data using parallel and perpendicular polarized 532 nm light combined with measured size distributions, and retrievals were performed using a genetic algorithm and Mie-Lorenz scattering theory. The absolute error associated with the m(r) retrieval is ±0.03, and reliable retrievals are possible for mass concentrations above 5-20 μg/m(3) depending on particle size. The limonene SOA data suggest the most important factor controlling the refractive index is the HC/NO(x) ratio; the refractive index is much less sensitive to the aerosol age or mass concentration. The refractive index ranges from about 1.34 to 1.56 for limonene and from 1.36 to 1.52 for α-pinene, and generally decreases as the HC/NO(x) ratio increases. Especially for limonene, the particle diameter is also inversely related to the HC/NO(x) ratio; the final size mode increases from 220 to 330 nm as the HC/NO(x) ratio decreases from 33 to 6. In an effort to explore the ability of models from the literature to explain the observed refractive indices, a recent limonene oxidation mechanism was combined with SOA partitioning and a structure-property relationship for estimating refractive indices of condensing species. The resulting refractive indices fell in a much narrower range (1.475 ± 0.02) of m(r) than observed experimentally. We hypothesize the experimentally observed high m(r) values are due to oligomerization and the low values to water uptake, small soluble molecules such as glyoxal and other factors, each of which is not included in the oxidation mechanism. Aerosol formation yields were measured over the mass concentration range from 6 to ∼150 μg/m(3), over which they increased steadily, and were higher for high HC/NO(x) ratio experiments.

Photoprotective Strategies of Mediterranean Plants in Relation to Morphological Traits and Natural Environmental Pressure: A Meta-Analytical Approach

PubMed Central

Fernández-Marín, Beatriz; Hernández, Antonio; Garcia-Plazaola, Jose I.; Esteban, Raquel; Míguez, Fátima; Artetxe, Unai; Gómez-Sagasti, Maria T.

2017-01-01

Despite being a small geographic extension, Mediterranean Basin is characterized by an exceptional plant biodiversity. Adaptive responses of this biocoenosis are delineated by an unusual temporal dissociation along the year between optimal temperature for growth and water availability. This fact generates the combination of two environmental stress factors: a period of summer drought, variable in length and intensity, and the occurrence of mild to cold winters. Both abiotic factors, trigger the generation of (photo)oxidative stress and plants orchestrate an arsenal of structural, physiological, biochemical, and molecular mechanisms to withstand such environmental injuries. In the last two decades an important effort has been made to characterize the adaptive morphological and ecophysiological traits behind plant survival strategies with an eye to predict how they will respond to future climatic changes. In the present work, we have compiled data from 89 studies following a meta-analytical approach with the aim of assessing the composition and plasticity of photosynthetic pigments and low-molecular-weight antioxidants (tocopherols, glutathione, and ascorbic acid) of wild Mediterranean plant species. The influence of internal plant and leaf factors on such composition together with the stress responsiveness, were also analyzed. This approach enabled to obtain data from 73 species of the Mediterranean flora, with the genus Quercus being the most frequently studied. Main highlights of present analysis are: (i) sort of photoprotective mechanisms do not differ between Mediterranean plants and other floras but they show higher plasticity indexes; (ii) α−tocopherol among the antioxidants and violaxanthin-cycle pigments show the highest responsiveness to environmental factors; (iii) both winter and drought stresses induce overnight retention of de-epoxidised violaxanthin-cycle pigments; (iv) this retention correlates with depressions of Fv/Fm; and (v) contrary to what could be expected, mature leaves showed higher accumulation of hydrophilic antioxidants than young leaves, and sclerophyllous leaves higher biochemical photoprotective demand than membranous leaves. In a global climatic change scenario, the plasticity of their photoprotective mechanisms will likely benefit Mediterranean species against oceanic ones. Nevertheless, deep research of ecoregions other than the Mediterranean Basin will be needed to fully understand photoprotection strategies of this extremely biodiverse floristic biome: the Mediterranean ecosystem. PMID:28674548

CORONA-INDUCED OZONATION COUPLED WITH PHOTOOXIDATION: AN ENVIRONMENTALLY FRIENDLY AND COST-EFFECTIVE METHOD

EPA Science Inventory

We have developed a process that uses surface corona for the production of ozone by passing air or oxygen through a high voltage electrical discharge and the emitted ultraviolet light is being used to activate a photocatalyst. A thin film of nanostructured TiO2 with primary part...

GAS AND PARTICULATE PRODUCTS DISTRIBUTION FROM THE PHOTOOXIDATION OF ALPHA-HUMULENE IN THE PRESENCE OF NOX, NATURAL ATMOSPHERIC AIR AND SUNLIGHT. (R828176)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

A COMPARISON OF URINARY ARSENIC SPECIATION VIA DIRECT NEBULIZATION AND ON-LINE PHOTOOXIDATION-HYDRIDE GENERATION WITH DETECTION BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Arsenic speciation continues to be important in assessing human and environmental exposure risk. Urinary arsenic analysis provides information on recent arsenic exposure. In this study, two sample introduction pathways: direct nebulization (DN) and hydride generation (HG) were ut...

Effects of Acifluorfen on Endogenous Antioxidants and Protective Enzymes in Cucumber (Cucumis sativus L.) Cotyledons

PubMed Central

Kenyon, William H.; Duke, Stephen O.

1985-01-01

The herbicide acifluorfen (2-chloro-4-(trifluoromethyl)phenoxy-2-nitrobenzoate) causes strong photooxidative destruction of pigments and lipids in sensitive plant species. Antioxidants and oxygen radical scavengers slow the bleaching action of the herbicide. The effect of acifluorfen on glutathione and ascorbate levels in cucumber (Cucumis sativus L.) cotyledon discs was investigated to assess the relationship between herbicide activity and endogenous antioxidants. Acifluorfen decreased the levels of glutathione and ascorbate over 50% in discs exposed to less than 1.5 hours of white light (450 microeinsteins per square meter per second). Coincident increases in dehydroascorbate and glutathione disulfide were not observed. Acifluorfen also caused the rapid depletion of ascorbate in far-red light grown plants which were photosynthetically incompetent. Glutathione reductase, dehydroascorbate reductase, superoxide dismutase, ascorbate oxidase, ascorbate free radical reductase, peroxidase, and catalase activities rapidly decreased in acifluorfen-treated tissue exposed to white light. None of the enzymes were inhibited in vitro by the herbicide. Acifluorfen causes irreversible photooxidative destruction of plant tissue, in part, by depleting endogenous antioxidants and inhibiting the activities of protective enzymes. PMID:16664506

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Kinetic concepts to quantify the role of oxidants and photooxidants in natural waters and water treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoigne, J.

1995-12-31

Research performed during the last two decades has led to a significant evolution of reaction kinetic concepts to estimate the role of reactive oxidants and photooxidants in natural waters and for water treatment. Although many reaction-rate data for oxidants such as OH and HO{sub 2}/O{sub 2}{sup -} radicals, O{sub 2} and O{sub 3} or ClO{sub 2} had been compiled before, these were rather selected to elucidate other areas of research and applications. Their critical applications for describing reactions of interest for aqueous chemistry has then required to extend the compilations of rate data: (1) to include more reactions of relevancemore » in aqueous media, (2) to critically account for the aqueous speciations, (3) to experimentally characterise the environmental factors controlling the steady-state concentration of different oxidants, (4) to formulate models useful for computing predictions and allowing for critical experimental tests, and (5) to allow for a unified concept for teaching environmental chemistry that better approaches the concepts of classical chemistry.« less

Optimization of Photosensitized Tryptophan Oxidation in the Presence of Dimegin-Polyvinylpyrrolidone-Chitosan Systems.

PubMed

Solovieva, Anna B; Kardumian, Valeria V; Aksenova, Nadezhda A; Belovolova, Lyudmila V; Glushkov, Mikhail V; Bezrukov, Evgeny A; Sukhanov, Roman B; Kotova, Svetlana L; Timashev, Peter S

2018-05-23

By the example of a model process of tryptophan photooxidation in the aqueous medium in the presence of a three-component photosensitizing complex (porphyrin photosensitizer-polyvinylpyrrolidone- chitosan, PPS-PVP-CT) in the temperature range of 20-40 °С, we have demonstrated a possibility of modification of such a process by selecting different molar ratios of the components in the reaction mixture. The actual objective of this selection is the formation of a certain PPS-PVP-CT composition in which PVP macromolecules would coordinate with PPS molecules and at the same time practically block the complex binding of PPS molecules with chitosan macromolecules. Such blocking allows utilization of the bactericidal properties of chitosan to a greater extent, since chitosan is known to depress the PPS photosensitizing activity in PPS-PVP-CT complexes when using those in photodynamic therapy (PDT). The optimal composition of photosensitizing complexes appears to be dependent on the temperature at which the PDT sessions are performed. We have analyzed the correlations of the effective rate constants of tryptophan photooxidation with the photophysical characteristics of the formed complexes.

Modeling of polymer photodegradation for solar cell modules

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1982-01-01

It was shown that many of the experimental observations in the photooxidation of hydrocarbon polymers can be accounted for with a computer simulation using an elementary mechanistic model with corresponding rate constants for each reaction. For outdoor applications, however, such as in photovoltaics, the variation of temperature must have important effects on the useful lifetimes of such materials. The data bank necessary to replace the isothermal rate constant values with Arrhenius activation parameters: A (the pre-exponential factor) and E (the activation energy) was searched. The best collection of data assembled to data is summarized. Note, however, that the problem is now considerably enlarged since from a theoretical point of view, with 51 of the input variables replaced with 102 parameters. The sensitivity of the overall scheme is such that even after many computer simulations, a successful photooxidation simulation with the expanded variable set was not completed. Many of the species in the complex process undergo a number of competitive pathways, the relative importance of each being often sensitive to small changes in the calculated rate constant values.

Synergies between Unsaturated Zn/Cu Doping Sites in Carbon Dots Provide New Pathways for Photocatalytic Oxidation

DOE PAGES

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin; ...

2017-12-07

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE PAGES

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; ...

2015-07-24

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Light-dark regulation of carotenoid biosynthesis in pepper (Capsicum annuum) leaves.

PubMed

Simkin, Andrew J; Zhu, Changfu; Kuntz, Marcel; Sandmann, Gerhard

2003-05-01

The carotenoid content in photosynthetic plant tissue reflects a steady state value resulting from permanent biosynthesis and concurrent photo-oxidation. The contributions of both reactions were determined in illuminated pepper leaves. The amount of carotenoids provided by biosynthesis were quantified by the accumulation of the colourless carotenoid phytoene in the presence of the inhibitor norflurazon. When applied, substantial amounts of this rather photo-stable intermediate were formed in the light. However, carotenoid biosynthesis was completely stalled in darkness. This switch off in the absence of light is related to the presence of very low messenger levels of the phytoene synthase gene, psy and the phytoene desaturase gene, pds. Other carotenogenic genes, such as zds, ptox and Icy-b also were shown to be down-regulated to some extent. By comparison of the carotenoid concentration before and after transfer of plants to increasing light intensities and accounting for the contribution of biosynthesis, the rate of photo-oxidation was estimated for pepper leaves. It could be demonstrated that light-independent degradation or conversion of carotenoids e.g. to abscisic acid is a minor process.

Photodegradation of imidacloprid insecticide by Ag-deposited titanate nanotubes: a study of intermediates and their reaction pathways.

PubMed

Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

2014-12-31

The present work demonstrates the influence of Ag-loading (0.2-1.0 wt %) onto sodium titanate nanotubes (TNT) for complete photomineralization of the neurotoxic imidacloprid (IMI) insecticide under UV light illumination. It has been observed that degradation of IMI follows pseudo-first-order kinetics, where 0.5 wt % Ag-loaded TNT exhibited highest apparent rate constant (2.2 × 10(-2) min(-1)) and corresponding least half-life (t1/2) of 31 min for IMI relative to bare P25-TiO2 (3.4 × 10(-3) min(-1), t1/2 = 230 min). The mineralization of IMI intermediates to CO2 during its photooxidation has been described by time course GC-MS and GC analysis and has been correlated with the kinetic analysis. The investigation for the role and quantitative estimation of the fate of heteroatoms (N, O, and Cl) present in IMI revealed an increase in the amount of nitrate, nitrite, and chloride ions with time during its photooxidation. On the basis of these results a mechanistic pathway for photomineralization of IMI is proposed.

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor.

PubMed

Rodríguez, Sylian; Almquist, Catherine; Lee, Tai Gyu; Furuuchi, Masami; Hedrick, Elizabeth; Biswas, Pratim

2004-02-01

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.

Near-IR squaraine dye–loaded gated periodic mesoporous organosilica for photo-oxidation of phenol in a continuous-flow device

PubMed Central

Borah, Parijat; Sreejith, Sivaramapanicker; Anees, Palapuravan; Menon, Nishanth Venugopal; Kang, Yuejun; Ajayaghosh, Ayyappanpillai; Zhao, Yanli

2015-01-01

Periodic mesoporous organosilica (PMO) has been widely used for the fabrication of a variety of catalytically active materials. We report the preparation of novel photo-responsive PMO with azobenzene-gated pores. Upon activation, the azobenzene gate undergoes trans-cis isomerization, which allows an unsymmetrical near-infrared squaraine dye (Sq) to enter into the pores. The gate closure by cis-trans isomerization of the azobenzene unit leads to the safe loading of the monomeric dye inside the pores. The dye-loaded and azobenzene-gated PMO (Sq-azo@PMO) exhibits excellent generation of reactive oxygen species upon excitation at 664 nm, which can be effectively used for the oxidation of phenol into benzoquinone in aqueous solution. Furthermore, Sq-azo@PMO as the catalyst was placed inside a custom-built, continuous-flow device to carry out the photo-oxidation of phenol to benzoquinone in the presence of 664-nm light. By using the device, about 23% production of benzoquinone with 100% selectivity was achieved. The current research presents a prototype of transforming heterogeneous catalysts toward practical use. PMID:26601266

Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Lu; Kollman, Matthew S.; Song, Chen

2014-01-28

The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways. The volatility and oxidation state of isoprene SOA is sensitive to and displays a non-linear dependence on NOx levels. When initial NO/isoprene ratio is approximately 3 (ppbv:ppbv), SOA are shown to be most oxidized and least volatile, associated with the highest SOA yield. A High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) is appliedmore » to characterize the key chemical properties of aerosols. While the composition of SOA in mixed experiments does not change substantially over time, SOA become less volatile and more oxidized as oxidation progresses in HO2-dominant experiments. Analysis of the SOA composition suggests that the further reactions of organic peroxides and alcohols may produce carboxylic acids, which might play a strong role in SOA aging.« less

Calcium Ligation in Photosystem II under Inhibiting Conditions

PubMed Central

Barry, Bridgette A.; Hicks, Charles; De Riso, Antonio; Jenson, David L.

2005-01-01

In oxygenic photosynthesis, PSII carries out the oxidation of water and reduction of plastoquinone. The product of water oxidation is molecular oxygen. The water splitting complex is located on the lumenal side of the PSII reaction center and contains manganese, calcium, and chloride. Four sequential photooxidation reactions are required to generate oxygen from water; the five sequentially oxidized forms of the water splitting complex are known as the Sn states, where n refers to the number of oxidizing equivalents stored. Calcium plays a role in water oxidation; removal of calcium is associated with an inhibition of the S state cycle. Although calcium can be replaced by other cations in vitro, only strontium maintains activity, and the steady-state rate of oxygen evolution is decreased in strontium-reconstituted PSII. In this article, we study the role of calcium in PSII that is limited in water content. We report that strontium substitution or 18OH2 exchange causes conformational changes in the calcium ligation shell. The conformational change is detected because of a perturbation to calcium ligation during the S1 to S2 and S2 to S3 transition under water-limited conditions. PMID:15985425

Coupling photochemical reaction detection based on singlet oxygen sensitization to capillary electrochromatography

PubMed

Dickson; Odom; Ducheneaux; Murray; Milofsky

2000-07-15

Despite the impressive separation efficiency afforded by capillary electrochromatography (CEC), the detection of UV-absorbing compounds following separation in capillary dimensions remains limited by the short path length (5-75 microm) through the column. Moreover, analytes that are poor chromophores present an additional challenge with respect to sensitive detection in CEC. This paper illustrates a new photochemical reaction detection scheme for CEC that takes advantage of the catalytic nature of type II photooxidation reactions. The sensitive detection scheme is selective toward molecules capable of photosensitizing the formation of singlet molecular oxygen (1O2). Following separation by CEC, UV-absorbing analytes promote groundstate 3O2 to an excited state (1O2) which reacts rapidly with tert-butyl-3,4,5-trimethylpyrrolecarboxylate, which is added to the running buffer. Detection is based on the loss of pyrrole. The reaction is catalytic in nature since one analyte molecule may absorb light many times, producing large amounts of 1O2. The detection limit for 9-acetylanthracene, following separation by CEC, is approximately 6 x 10(-9) M (S/N = 3). Optimization of the factors effecting the S/N for four model compounds is discussed.

Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

PubMed

Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

2016-12-01

In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

Unified mechanism of the surface Fermi level pinning in III-As nanowires.

PubMed

Alekseev, Prokhor A; Dunaevskiy, Mikhail S; Cirlin, George E; Reznik, Rodion R; Smirnov, Alexander N; Kirilenko, Demid A; Davydov, Valery Yu; Berkovits, Vladimir L

2018-08-03

Fermi level pinning at the oxidized (110) surfaces of III-As nanowires (GaAs, InAs, InGaAs, AlGaAs) is studied. Using scanning gradient Kelvin probe microscopy, we show that the Fermi level at oxidized cleavage surfaces of ternary Al x Ga 1-x As (0 ≤ x ≤ 0.45) and Ga x In 1-x As (0 ≤ x ≤ 1) alloys is pinned at the same position of 4.8 ± 0.1 eV with regard to the vacuum level. The finding implies a unified mechanism of the Fermi level pinning for such surfaces. Further investigation, performed by Raman scattering and photoluminescence spectroscopy, shows that photooxidation of the Al x Ga 1-x As and Ga x In 1-x As nanowires leads to the accumulation of an excess of arsenic on their crystal surfaces which is accompanied by a strong decrease of the band-edge photoluminescence intensity. We conclude that the surface excess arsenic in crystalline or amorphous forms is responsible for the Fermi level pinning at oxidized (110) surfaces of III-As nanowires.

Cross-talk between cognate and noncognate RpoE sigma factors and Zn(2+)-binding anti-sigma factors regulates photooxidative stress response in Azospirillum brasilense.

PubMed

Gupta, Namrata; Gupta, Ankush; Kumar, Santosh; Mishra, Rajeev; Singh, Chhaya; Tripathi, Anil Kumar

2014-01-01

Azospirillum brasilense harbors two redox-sensitive Zinc-binding anti-sigma (ZAS) factors (ChrR1 and ChrR2), which negatively regulate the activity of their cognate extra-cytoplasmic function (ECF) σ factors (RpoE1 and RpoE2) by occluding their binding to the core enzyme. Both pairs of RpoE-ChrR control responses to photooxidative stress. The aim of this study was to investigate whether the two RpoE-ChrR pairs cross-talk while responding to the stress. In silico analysis showed a high sequence similarity between ChrR1 and ChrR2 proteins, but differences in redox sensitivity. Using in silico and in vitro methods of protein-protein interaction, we have shown that both ChrR1 and ChrR2 proteins physically bind to their noncognate RpoE proteins. Restoration of the phenotypes of chrR1::Tn5 and chrR2::Km mutants related to carotenoid biosynthesis and photooxidative stress tolerance by expressing chrR1 or chrR2 provided in vivo evidence for the cross-talk. In addition, up- or down-regulation of several identical proteins by expressing chrR1 or chrR2 in the chrR1::Tn5 mutant provided another in vivo evidence for the cross-talk. Although multiple redox-sensitive ZAS anti-σ factors occur in some Gram-positive bacteria, no cross-talk is reported among them. We report here, for the first time, that the two ZAS anti-σ factors of A. brasilense also interact with their noncognate σ factors and affect gene expression. The two redox-sensitive ZAS anti-σ factors in A. brasilense may interact with their cognate as well as noncognate ECF σ factors to play an important role in redox homeostasis by facilitating recovery from the oxidative stress.

Inflammatory responses to secondary organic aerosols (SOA) generated from biogenic and anthropogenic precursors

NASA Astrophysics Data System (ADS)

Tuet, Wing Y.; Chen, Yunle; Fok, Shierly; Champion, Julie A.; Ng, Nga L.

2017-09-01

Cardiopulmonary health implications resulting from exposure to secondary organic aerosols (SOA), which comprise a significant fraction of ambient particulate matter (PM), have received increasing interest in recent years. In this study, alveolar macrophages were exposed to SOA generated from the photooxidation of biogenic and anthropogenic precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different formation conditions (RO2 + HO2 vs. RO2 + NO dominant, dry vs. humid). Various cellular responses were measured, including reactive oxygen and nitrogen species (ROS/RNS) production and secreted levels of cytokines, tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6). SOA precursor identity and formation condition affected all measured responses in a hydrocarbon-specific manner. With the exception of naphthalene SOA, cellular responses followed a trend where TNF-α levels reached a plateau with increasing IL-6 levels. ROS/RNS levels were consistent with relative levels of TNF-α and IL-6, due to their respective inflammatory and anti-inflammatory effects. Exposure to naphthalene SOA, whose aromatic-ring-containing products may trigger different cellular pathways, induced higher levels of TNF-α and ROS/RNS than suggested by the trend. Distinct cellular response patterns were identified for hydrocarbons whose photooxidation products shared similar chemical functionalities and structures, which suggests that the chemical structure (carbon chain length and functionalities) of photooxidation products may be important for determining cellular effects. A positive nonlinear correlation was also detected between ROS/RNS levels and previously measured DTT (dithiothreitol) activities for SOA samples. In the context of ambient samples collected during summer and winter in the greater Atlanta area, all laboratory-generated SOA produced similar or higher levels of ROS/RNS and DTT activities. These results suggest that the health effects of SOA are important considerations for understanding the health implications of ambient aerosols.

Phytohormone Interaction Modulating Fruit Responses to Photooxidative and Heat Stress on Apple (Malus domestica Borkh.).

PubMed

Torres, Carolina A; Sepúlveda, Gloria; Kahlaoui, Besma

2017-01-01

Sun-related physiological disorders such as sun damage on apples ( Malus domestica Borkh) are caused by cumulative photooxidative and heat stress during their growing season triggering morphological, physiological, and biochemical changes in fruit tissues not only while it is on the tree but also after it has been harvested. The objective of the work was to establish the interaction of auxin (indole-3-acetic acid; IAA), abscisic acid (ABA), jasmonic acid (JA), salicylic acid (SA), and ethylene (ET) and its precursor ACC (free and conjugated, MACC) during development of sun-injury-related disorders pre- and post-harvest on apples. Peel tissue was extracted from fruit growing under different sun exposures (Non-exposed, NE; Exposed, EX) and with sun injury symptoms (Moderate, Mod). Sampling was carried out every 15 days from 75 days after full bloom (DAFB) until 120 days post-harvest in cold storage (1°C, > 90%RH). Concentrations of IAA, ABA, JA, SA, were determined using UHPLC mass spectrometry, and ET and ACC (free and conjugated MACC) using gas chromatography. IAA was found not to be related directly to sun injury development, but it decreased 60% in sun exposed tissue, and during fruit development. ABA, JA, SA, and ethylene concentrations were significantly higher ( P ≤ 0.05) in Mod tissue, but their concentration, except for ethylene, were not affected by sun exposure. ACC and MACC concentrations increased until 105 DAFB in all sun exposure categories. During post-harvest, ethylene climacteric peak was delayed on EX compared to Mod. ABA and SA concentrations remained stable throughout storage in both tissue. JA dramatically increased post-harvest in both EX and Mod tissue, and orchards, confirming its role in low temperature tolerance. The results suggest that ABA, JA, and SA together with ethylene are modulating some of the abiotic stress defense responses on sun-exposed fruit during photooxidative and heat stress on the tree.

Phytohormone Interaction Modulating Fruit Responses to Photooxidative and Heat Stress on Apple (Malus domestica Borkh.)

PubMed Central

Torres, Carolina A.; Sepúlveda, Gloria; Kahlaoui, Besma

2017-01-01

Sun-related physiological disorders such as sun damage on apples (Malus domestica Borkh) are caused by cumulative photooxidative and heat stress during their growing season triggering morphological, physiological, and biochemical changes in fruit tissues not only while it is on the tree but also after it has been harvested. The objective of the work was to establish the interaction of auxin (indole-3-acetic acid; IAA), abscisic acid (ABA), jasmonic acid (JA), salicylic acid (SA), and ethylene (ET) and its precursor ACC (free and conjugated, MACC) during development of sun-injury-related disorders pre- and post-harvest on apples. Peel tissue was extracted from fruit growing under different sun exposures (Non-exposed, NE; Exposed, EX) and with sun injury symptoms (Moderate, Mod). Sampling was carried out every 15 days from 75 days after full bloom (DAFB) until 120 days post-harvest in cold storage (1°C, > 90%RH). Concentrations of IAA, ABA, JA, SA, were determined using UHPLC mass spectrometry, and ET and ACC (free and conjugated MACC) using gas chromatography. IAA was found not to be related directly to sun injury development, but it decreased 60% in sun exposed tissue, and during fruit development. ABA, JA, SA, and ethylene concentrations were significantly higher (P ≤ 0.05) in Mod tissue, but their concentration, except for ethylene, were not affected by sun exposure. ACC and MACC concentrations increased until 105 DAFB in all sun exposure categories. During post-harvest, ethylene climacteric peak was delayed on EX compared to Mod. ABA and SA concentrations remained stable throughout storage in both tissue. JA dramatically increased post-harvest in both EX and Mod tissue, and orchards, confirming its role in low temperature tolerance. The results suggest that ABA, JA, and SA together with ethylene are modulating some of the abiotic stress defense responses on sun-exposed fruit during photooxidative and heat stress on the tree. PMID:29491868

Assessment of the reduction methods used to develop chemical schemes: building of a new chemical scheme for VOC oxidation suited to three-dimensional multiscale HOx-NOx-VOC chemistry simulations

NASA Astrophysics Data System (ADS)

Szopa, S.; Aumont, B.; Madronich, S.

2005-09-01

The objective of this work was to develop and assess an automatic procedure to generate reduced chemical schemes for the atmospheric photooxidation of volatile organic carbon (VOC) compounds. The procedure is based on (i) the development of a tool for writing the fully explicit schemes for VOC oxidation (see companion paper Aumont et al., 2005), (ii) the application of several commonly used reduction methods to the fully explicit scheme, and (iii) the assessment of resulting errors based on direct comparison between the reduced and full schemes.

The reference scheme included seventy emitted VOCs chosen to be representative of both anthropogenic and biogenic emissions, and their atmospheric degradation chemistry required more than two million reactions among 350000 species. Three methods were applied to reduce the size of the reference chemical scheme: (i) use of operators, based on the redundancy of the reaction sequences involved in the VOC oxidation, (ii) grouping of primary species having similar reactivities into surrogate species and (iii) grouping of some secondary products into surrogate species. The number of species in the final reduced scheme is 147, this being small enough for practical inclusion in current three-dimensional models. Comparisons between the fully explicit and reduced schemes, carried out with a box model for several typical tropospheric conditions, showed that the reduced chemical scheme accurately predicts ozone concentrations and some other aspects of oxidant chemistry for both polluted and clean tropospheric conditions.

THE PHOTOCATALYTIC OXIDATION OF LOW CONCENTRATION MTBE ON TITANIUM DIOXIDE FROM GROUNDWATER IN A FALLING FILM REACTOR

EPA Science Inventory

This study focuses on three objectives: 1) to determine the feasibility of using a falling-film slurry photocatalytic reactor for the degradation of MTBE in water, 2) to assess the feasibility of MTBE photo-oxidation on TiO2 at low initial MTBE concentrations (<10 mg/L), and 3) t...

DETERMINATION OF 2-METHYL TETROLS AND 2-METHYLGLYCERIC ACID IN SECONDARY ORGANIC AEROSOL FROM LABORATORY IRRADIATED ISOPRENE/NO X/SO 2/AIR MIXTURES

EPA Science Inventory

This presentation addresses recent work performed at EPA to evaluate the potential for the photooxidation of isoprene to produce secondary organic aerosol. Analysis of the samples for methyl tetrols and 2-methylglyceric acid were performed at EPA and the University of Antwerp. T...

Stabilized unsaturated polyesters

NASA Technical Reports Server (NTRS)

Vogl, O.; Borsig, E. (Inventor)

1985-01-01

An unsaturated polyester, such as propylene glycolmaleic acid phthalic acid prepolymer dissolved in styrene is interpolymerized with an ultraviolet absorber and/or an antioxidant. The unsaturated chain may be filled with H or lower alkyl such as methyl and tertiary alkyl such as tertiary butyl. A polymer stable to exposure to the outdoors without degradation by ultraviolet radiation, thermal and/or photooxidation is formed.

Comparison of different stomatal conductance algorithms for ozone flux modelling [Proceedings

Treesearch

P. Buker; L. D. Emberson; M. R. Ashmore; G. Gerosa; C. Jacobs; W. J. Massman; J. Muller; N. Nikolov; K. Novak; E. Oksanen; D. De La Torre; J. -P. Tuovinen

2006-01-01

The ozone deposition model (D03SE) that has been developed and applied within the EMEP photooxidant model (Emberson et al., 2000, Simpson et al. 2003) currently estimates stomatal ozone flux using a stomatal conductance (gs) model based on the multiplicative algorithm initially developed by Jarvis (1976). This model links gs to environmental and phenological parameters...

Lutein and zeaxanthin supplementation reduces photo-oxidative damage and modulates the expression of inflammation related genes in retinal pigment epithelial cells

USDA-ARS?s Scientific Manuscript database

Oxidative damage and inflammation are related to the pathogenesis of age-related macular degeneration (AMD). Epidemiologic studies suggest that insufficient dietary lutein and zeaxanthin intake or lower serum zeaxanthin levels are associated with increased risk for AMD. The objective of this work w...

The Protective Role of Antioxidants in the Defence against ROS/RNS-Mediated Environmental Pollution

PubMed Central

Poljšak, Borut; Fink, Rok

2014-01-01

Overproduction of reactive oxygen and nitrogen species can result from exposure to environmental pollutants, such as ionising and nonionising radiation, ultraviolet radiation, elevated concentrations of ozone, nitrogen oxides, sulphur dioxide, cigarette smoke, asbestos, particulate matter, pesticides, dioxins and furans, polycyclic aromatic hydrocarbons, and many other compounds present in the environment. It appears that increased oxidative/nitrosative stress is often neglected mechanism by which environmental pollutants affect human health. Oxidation of and oxidative damage to cellular components and biomolecules have been suggested to be involved in the aetiology of several chronic diseases, including cancer, cardiovascular disease, cataracts, age-related macular degeneration, and aging. Several studies have demonstrated that the human body can alleviate oxidative stress using exogenous antioxidants. However, not all dietary antioxidant supplements display protective effects, for example, β-carotene for lung cancer prevention in smokers or tocopherols for photooxidative stress. In this review, we explore the increases in oxidative stress caused by exposure to environmental pollutants and the protective effects of antioxidants. PMID:25140198

Photochemical oxidants: state of the science.

PubMed

Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

1999-01-01

Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

Particulate and gas-phase products from the atmospheric degradation of chlorpyrifos and chlorpyrifos-oxon

NASA Astrophysics Data System (ADS)

Borrás, Esther; Ródenas, Milagros; Vázquez, Mónica; Vera, Teresa; Muñoz, Amalia

2015-12-01

The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product - chlorpyrifos-oxon - are described. The photo-oxidation under the presence of NOx was studied in a large outdoor simulation chamber for both chlorpyrifos and chlorpyrifos-oxon, observing a rapid degradation (Half lifetime < 3.5 h for both compounds). Also, the photolysis reactions of both were studied. The formation of particulate matter (aerosol mass yield ranged 6-59%) and gaseous products were monitored. The chemical composition of minor products was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as 3,5,6-trichloropyridin-2-ol and ethyl 3,5,6-trichloropyridin-2-yl hydrogen phosphate. An atmospheric degradation mechanism has been amplified based on an oxidation started with OH-nucleophilic attack to Pdbnd S bond.

Coulomb couplings in solubilised light harvesting complex II (LHCII): challenging the ideal dipole approximation from TDDFT calculations.

PubMed

López-Tarifa, P; Liguori, Nicoletta; van den Heuvel, Naudin; Croce, Roberta; Visscher, Lucas

2017-07-19

The light harvesting complex II (LHCII), is a pigment-protein complex responsible for most of the light harvesting in plants. LHCII harvests sunlight and transfers excitation energy to the reaction centre of the photo-system, where the water oxidation process takes place. The energetics of LHCII can be modulated by means of conformational changes allowing a switch from a harvesting to a quenched state. In this state, the excitation energy is no longer transferred but converted into thermal energy to prevent photooxidation. Based on molecular dynamics simulations at the microsecond time scale, we have recently proposed that the switch between different fluorescent states can be probed by correlating shifts in the chromophore-chromophore Coulomb interactions to particular protein movements. However, these findings are based upon calculations in the ideal point dipole approximation (IDA) where the Coulomb couplings are simplified as first order dipole-dipole interactions, also assuming that the chromophore transition dipole moments lay in particular directions of space with constant moduli (FIX-IDA). In this work, we challenge this approximation using the time-dependent density functional theory (TDDFT) combined with the frozen density embedding (FDE) approach. Our aim is to establish up to which limit FIX-IDA can be applied and which chromophore types are better described under this approximation. For that purpose, we use the classical trajectories of solubilised light harvesting complex II (LHCII) we have recently reported [Liguori et al., Sci. Rep., 2015, 5, 15661] and selected three pairs of chromophores containing chlorophyll and carotenoids (Chl and Car): Chla611-Chla612, Chlb606-Chlb607 and Chla612-Lut620. Using the FDE in the Tamm-Dancoff approximation (FDEc-TDA), we show that IDA is accurate enough for predicting Chl-Chl Coulomb couplings. However, the FIX-IDA largely overestimates Chl-Car interactions mainly because the transition dipole for the Cars is not trivially oriented on the polyene chain.

Photo-oxidation of tyrosine in a bio-engineered bacterioferritin 'reaction centre'-a protein model for artificial photosynthesis.

PubMed

Hingorani, Kastoori; Pace, Ron; Whitney, Spencer; Murray, James W; Smith, Paul; Cheah, Mun Hon; Wydrzynski, Tom; Hillier, Warwick

2014-10-01

The photosynthetic reaction centre (RC) is central to the conversion of solar energy into chemical energy and is a model for bio-mimetic engineering approaches to this end. We describe bio-engineering of a Photosystem II (PSII) RC inspired peptide model, building on our earlier studies. A non-photosynthetic haem containing bacterioferritin (BFR) from Escherichia coli that expresses as a homodimer was used as a protein scaffold, incorporating redox-active cofactors mimicking those of PSII. Desirable properties include: a di-nuclear metal binding site which provides ligands for bivalent metals, a hydrophobic pocket at the dimer interface which can bind a photosensitive porphyrin and presence of tyrosine residues proximal to the bound cofactors, which can be utilised as efficient electron-tunnelling intermediates. Light-induced electron transfer from proximal tyrosine residues to the photo-oxidised ZnCe6(•+), in the modified BFR reconstituted with both ZnCe6 and Mn(II), is presented. Three site-specific tyrosine variants (Y25F, Y58F and Y45F) were made to localise the redox-active tyrosine in the engineered system. The results indicate that: presence of bound Mn(II) is necessary to observe tyrosine oxidation in all BFR variants; Y45 the most important tyrosine as an immediate electron donor to the oxidised ZnCe6(•+) and that Y25 and Y58 are both redox-active in this system, but appear to function interchangebaly. High-resolution (2.1Å) crystal structures of the tyrosine variants show that there are no mutation-induced effects on the overall 3-D structure of the protein. Small effects are observed in the Y45F variant. Here, the BFR-RC represents a protein model for artificial photosynthesis. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Antioxidant defences and oxidative damage in salt-treated olive plants under contrasting sunlight irradiance.

PubMed

Melgar, Juan Carlos; Guidi, Lucia; Remorini, Damiano; Agati, Giovanni; Degl'innocenti, Elena; Castelli, Silvana; Camilla Baratto, Maria; Faraloni, Cecilia; Tattini, Massimiliano

2009-09-01

The interactive effects of root-zone salinity and sunlight on leaf biochemistry, with special emphasis on antioxidant defences, were analysed in Olea europaea L. cv. Allora, during the summer period. Plants were grown outside under 15% (shade plants) or 100% sunlight (sun plants) and supplied with 0 or 125 mM NaCl. The following measurements were performed: (1) the contribution of ions and soluble carbohydrates to osmotic potentials; (2) the photosystem II (PSII) photochemistry and the photosynthetic pigment concentration; (3) the concentration and the tissue-specific distribution of leaf flavonoids; (4) the activity of antioxidant enzymes; and (5) the leaf oxidative damage. The concentrations of Na(+) and Cl(-) were significantly greater in sun than in shade leaves, as also observed for the concentration of the 'antioxidant' sugar-alcohol mannitol. The de-epoxidation state of violaxanthin-cycle pigments increased in response to salinity stress in sun leaves. This finding agrees with a greater maximal PSII photochemistry (F(v)/F(m)) at midday, detected in salt-treated than in control plants, growing in full sunshine. By contrast, salt-treated plants in the shade suffered from midday depression in F(v)/F(m) to a greater degree than that observed in control plants. The high concentration of violaxanthin-cycle pigments in sun leaves suggests that zeaxanthin may protect the chloroplast from photo-oxidative damage, rather than dissipating excess excitation energy via non-photochemical quenching mechanisms. Dihydroxy B-ring-substituted flavonoid glycosides accumulate greatly in the mesophyll, not only in the epidermal cells, in response to high sunlight. The activity of antioxidant enzymes varied little because of sunlight irradiance, but declined sharply in response to high salinity in shade leaves. Interestingly, control and particularly salt-treated plants in the shade underwent greater oxidative damage than their sunny counterparts. These findings, which conform to the evolution of O. europaea in sunny environments, suggest that under partial shading, the antioxidant defence system may be ineffective to counter salt-induced oxidative damage.

Photooxidation of farnesene mixtures in the presence of NOx: Analysis of reaction products and their implication to ambient PM2.5

EPA Science Inventory

Chemical analysis of SOA produced from the irradiation of a mixture of α/β-farnesene/NOx was conducted in a 14.5 m3 smog chamber. SOA collected on glass-fiber filters was solvent extracted, derivatized using BSTFA, and analyzed by GC–MS. Gas-phase products were a...

PHOTOOXIDATION OF TOLUENE AND P-XYLENE IN CATION-EXCHANGED ZEOLITES X, Y, ZSM-5, AND BETA: THE ROLE OF ZEOLITE PHYSICOCHEMICAL PROPERTIES IN PRODUCT YIELD AND SELECTIVITY. (R825304)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Photooxidation of chloride by oxide minerals: implications for perchlorate on Mars.

PubMed

Schuttlefield, Jennifer D; Sambur, Justin B; Gelwicks, Melissa; Eggleston, Carrick M; Parkinson, B A

2011-11-09

We show that highly oxidizing valence band holes, produced by ultraviolet (UV) illumination of naturally occurring semiconducting minerals, are capable of oxidizing chloride ion to perchlorate in aqueous solutions at higher rates than other known natural perchlorate production processes. Our results support an alternative to atmospheric reactions leading to the formation of high concentrations of perchlorate on Mars.

Low Molecular Weight Carboxylic Acids in the Sea: Photooxidative Production and Biological Cycling

DTIC Science & Technology

1990-07-26

J.D. Burton, P.G. Brewer and R. Chesselet, Eds.). pp. 137-157, Plenum. 1987 Mo0per. K. and R.C. Zika. Free amino acids in marine rains: Evidence for...substrate for manyI The method Is based on the oxidation of formats by formate aerobic and anaerobic bacteria and for sonme yeasts (3) Jn dehydrogenase

Influence of process parameters on the effectiveness of photooxidative treatment of pharmaceuticals.

PubMed

Markic, Marinko; Cvetnic, Matija; Ukic, Sime; Kusic, Hrvoje; Bolanca, Tomislav; Bozic, Ana Loncaric

2018-03-21

In this study, UV-C/H 2 O 2 and UV-C/[Formula: see text] processes as photooxidative Advanced oxidation processes were applied for the treatment of seven pharmaceuticals, either already included in the Directive 2013/39/EU "watch list" (17α- ethynylestradiol, 17β-estradiol) or with potential to be added in the near future due to environmental properties and increasing consumption (azithromycin, carbamazepine, dexamethasone, erythromycin and oxytetracycline). The influence of process parameters (pH, oxidant concentration and type) on the pharmaceuticals degradation was studied through employed response surface modelling approach. It was established that degradation obeys first-order kinetic regime regardless structural differences and over entire range of studied process parameters. The results revealed that the effectiveness of UV-C/H 2 O 2 process is highly dependent on both initial pH and oxidant concentration. It was found that UV-C/[Formula: see text] process, exhibiting several times faster degradation of studied pharmaceuticals, is less sensitive to pH changes providing practical benefit to its utilization. The influence of water matrix on degradation kinetics of studied pharmaceuticals was studied through natural organic matter effects on single component and mixture systems.

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

PubMed

Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

2018-05-01

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Quantifying accessible sites and reactivity on titania–silica (photo)catalysts: Refining TOF calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eaton, Todd R.; Campos, Michael P.; Gray, Kimberly A.

2014-01-01

It can be difficult to determine the number of active atoms accessible to the fluid phase in mixed oxide catalysts, as required for obtaining true turnover frequencies (TOF). Here, we utilize the selective titration of surface Ti atoms with phenylphosphonic acid (PPA) on TiO 2–SiO 2 materials to estimate the number of reactant-accessible sites. TiO 2–SiO 2 composites were synthesized over a range of Ti loadings from grafting of titanocene dichloride (Cp 2TiCl 2) or tetraethoxy orthotitanate (TEOT) on SiO 2 and sol–gel co-hydrolysis of Si and Ti alkoxides. The materials were characterized by DRUV–vis, XRD, BET, and XANES. Despitemore » the significant morphological and electronic differences, materials prepared by Cp 2TiCl 2 and TEOT yielded a near-constant TOF of 0.14 h -1 (±0.04) across Ti loadings, for benzyl alcohol photooxidation, when normalizing rates by sites titrated by PPA. The fraction of Ti atoms titrated by PPA was strongly dependent on synthesis method and surface density. PPA titration and benzyl alcohol photooxidation may be useful measures of surface accessibility in other supported oxides.« less

Regional and long-range transport scenarios for photo-oxidants on the Mediterranean basin in summer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Millan, M.; Mantilla, E.; Salvador, R.

1996-12-31

Atmospheric research, begun in 1988, has shown that the dynamics of air pollutants in the Mediterranean basin in summer are governed by processes ranging from local to large meso-scale with diurnal cycles. Large scale convection over some regions, and up-slope winds in others, can inject aged pollutants into the Mid-troposphere, where they can participate in long-range processes within Southern and Central Europe. Two scenarios have been identified for the regional and long-range transport of photo-oxidants and other pollutants within, and out of, the Western Mediterranean basin. The first scenario involves the pollutants injected over the Spanish Central Plateau directly intomore » the mid-troposphere, and the second, the reservoir layers created along the Mediterranean coast. In the second scenario the key components are: the semi-permanent high(er) pressure area over the colder waters in the Gulf of Lion-Western Mediterranean basin, the mountain ranges which surround it, and the coastal processes. During the day the coastal circulations renovate the upper reservoir layers while the lower ones are drawn inland with the sea-breeze, and effective flow is mostly perpendicular to the coast.« less

Putting the Oxylipidome to Work: A Novel Lipidomics Pipeline Reveals Candidate Biomarkers for Photooxidative Stress in Phytoplankton

NASA Astrophysics Data System (ADS)

Collins, J.; Edwards, B. R.; Fredricks, H. F.; Van Mooy, B. A.

2016-02-01

The lipids of marine plankton encompass a diversity of biochemical functions and chemotaxonomic specificities that make them ideal molecular biomarkers in living biomass. While core, nonpolar lipids such as free fatty acids (FFA) have formed the basis for many biomarker studies in fresh biomass, methods that enable the simultaneous profiling of core lipids and intact polar lipids (IPL) have opened new avenues for characterization of environmental stressors. We demonstrate the application of a novel, rules-based lipidomics data analysis pipeline to putatively identify a broad range of intact polar lipids, intact oxidized lipids (ox-lipids) and oxylipins in accurate-mass HPLC-ESI-MS data. Using mass spectra from a lipid peroxidation experiment conducted under the natural, ultraviolet-enriched light field in West Antarctica, we use the pipeline to identify ox-lipid and oxylipin biomarkers that might serve as indicators of photooxidative stress in phytoplankton. The lipidomics pipeline derives much of its functionality from two boutique lipid-oxylipin databases, which together contain entries for more than 60,000 candidate lipid biomarkers. These databases and all scripts required by the pipeline will be publicly available online to other users.

Physiological Characteristics Underlying the Distribution Patterns of Luminous Bacteria in the Mediterranean Sea and the Gulf of Elat

PubMed Central

Shilo, M.; Yetinson, T.

1979-01-01

Physiological characteristics of luminous bacteria isolated from the Mediterranean and Gulf of Elat were compared to determine their relationship to the specific seasonal and geographic distribution patterns of these bacteria. The effects of temperature on growth rate and yield, relative sensitivity to photooxidation, resistance to high salt concentration (8%), and ability to grow in nutrient-poor conditions appear to control these patterns. The winter appearance of Photobacterium fischeri and the succession of winter and summer types of Beneckea harveyi in the eastern Mediterranean are explained by different temperature requirements for growth. Sensitivity to photooxidation explains the disappearance of P. leiognathi, present in the main body of the Gulf of Elat throughout the year, from the shallow coastal strip. B. harveyi is present in this coastal strip which is higher in nutrients and in productivity than the open waters. Competition experiments between B. harveyi and P. leiognathi in batch and continuous culture indicate that the oligotrophic P. leiognathi is outcompeted by B. harveyi in rich and even in relatively poor media. The distribution pattern found in the Bardawil hypersaline lagoon is explained by selection of salinity-resistant mutants of B. harveyi from the Mediterranean Sea. PMID:16345442

Sources of primary and secondary organic aerosols in Chinese versus European Cities during winter time

NASA Astrophysics Data System (ADS)

Prevot, A. S.; Slowik, J.; El-Haddad, I.; Pieber, S. M.; Yuan, B.; Stefenelli, G.; Pospisilova, V.; Lopez-Hilfiker, F.; Qi, L.; Tong, Y.; Wang, L.; Daellenbach, K.; Klein, F.; Elser, M.; Junji, C.; Huang, R. J. J.; Baltensperger, U.

2017-12-01

In the recent years, aerosol mass spectrometric (AMS) measurements were performed in Beijing (China), Zurich (Switzerland) and other Chinese and European cities indicating the importance of not only primary sources but also secondary organic aerosol (SOA) sources despite low radiation levels for photooxidation. Among the primary sources, residential burning is especially important in winter including wood and coal burning. Also for secondary organic aerosols, VOC emissions of residential burning are likely an important source in winter. An interesting question is whether daytime photooxidation and/or night-time NO3 radical chemistry are important pathways for the SOA formation. Recently we developed a new measurement technique based on exctractive electrospray ionization (EESI) that allow for the study of the organic molecules in the particulate phase without fragmentation. Combined measurements with AMS and EESI will be discussed for smogchamber experiments (simulating both nighttime and daytime chemistry) SOA formation potential, the link between VOCs and SOA and the SOA composition. In-situ and off-line measurements in Europe and China are analyzed in the light of those experiments with a focus on the importance of residential burning to both primary and secondary organic aerosols in cities during winter.

Ultrafast dynamics of the photo-excited hemes b and cn in the cytochrome b6f complex.

PubMed

Agarwal, Rachna; Chauvet, Adrien A P

2017-01-25

The dynamics of hemes b and c n within the cytochrome b 6 f complex are investigated by means of ultrafast broad-band transient absorption spectroscopy. On the one hand, the data reveal that, subsequent to visible light excitation, part of the b hemes undergoes pulse-limited photo-oxidation, with the liberated electron supposedly being transferred to one of the adjacent aromatic amino acids. Photo-oxidation is followed by charge recombination in about 8.2 ps. Subsequent to charge recombination, heme b is promoted to a vibrationally excited ground state that relaxes in about 4.6 ps. On the other hand, heme c n undergoes ultrafast ground state recovery in about 140 fs. Interestingly, the data also show that, in contrast to previous beliefs, Chl a is involved in the photochemistry of hemes. Indeed, subsequent to heme excitation, Chl a bleaches and recovers to its ground state in 90 fs and 650 fs, respectively. Chl a bleaching allegedly corresponds to the formation of a short lived Chl a anion. Beyond the previously suggested structural role, this study provides unique evidence that Chl a is directly involved in the photochemistry of the hemes.

Respiratory terminal oxidases alleviate photo-oxidative damage in photosystem I during repetitive short-pulse illumination in Synechocystis sp. PCC 6803.

PubMed

Shimakawa, Ginga; Miyake, Chikahiro

2018-03-08

Oxygenic phototrophs are vulnerable to damage by reactive oxygen species (ROS) that are produced in photosystem I (PSI) by excess photon energy over the demand of photosynthetic CO 2 assimilation. In plant leaves, repetitive short-pulse (rSP) illumination produces ROS to inactivate PSI. The production of ROS is alleviated by oxidation of the reaction center chlorophyll in PSI, P700, during the illumination with the short-pulse light, which is supported by flavodiiron protein (FLV). In this study, we found that in the cyanobacterium Synechocystis sp. PCC 6803 P700 was oxidized and PSI was not inactivated during rSP illumination even in the absence of FLV. Conversely, the mutant deficient in respiratory terminal oxidases was impaired in P700 oxidation during the illumination with the short-pulse light to suffer from photo-oxidative damage in PSI. Interestingly, the other cyanobacterium Synechococcus sp. PCC 7002 could not oxidize P700 without FLV during rSP illumination. These data indicate that respiratory terminal oxidases are critical to protect PSI from ROS damage during rSP illumination in Synechocystis sp. PCC 6803 but not Synechococcus sp. PCC 7002.

Photoprotection by foliar anthocyanins mitigates effects of boron toxicity in sweet basil (Ocimum basilicum).

PubMed

Landi, Marco; Guidi, Lucia; Pardossi, Alberto; Tattini, Massimiliano; Gould, Kevin S

2014-11-01

Boron (B) toxicity is an important agricultural problem in arid environments. Excess edaphic B compromises photosynthetic efficiency, limits growth and reduces crop yield. However, some purple-leafed cultivars of sweet basil (Ocimum basilicum) exhibit greater tolerance to high B concentrations than do green-leafed cultivars. We hypothesised that foliar anthocyanins protect basil leaf mesophyll from photo-oxidative stress when chloroplast function is compromised by B toxicity. Purple-leafed 'Red Rubin' and green-leafed 'Tigullio' cultivars, grown with high or negligible edaphic B, were given a photoinhibitory light treatment. Possible effects of photoabatement by anthocyanins were simulated by superimposing a purple polycarbonate filter on the green leaves. An ameliorative effect of light filtering on photosynthetic quantum yield and on photo-oxidative load was observed in B-stressed plants. In addition, when green protoplasts from both cultivars were treated with B and illuminated through a screen of anthocyanic protoplasts or a polycarbonate film which approximated cyanidin-3-O-glucoside optical properties, the degree of photoinhibition, hydrogen peroxide production, and malondialdehyde content were reduced. The data provide evidence that anthocyanins exert a photoprotective role in purple-leafed basil mesophyll cells, thereby contributing to improved tolerance to high B concentrations.

Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.

2014-12-01

Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.

Direct evidence for coastal iodine particles from Laminaria macroalgae - linkage to emissions of molecular iodine

NASA Astrophysics Data System (ADS)

McFiggans, G.; Coe, H.; Burgess, R.; Allan, J.; Cubison, M.; Alfarra, M. R.; Saunders, R.; Saiz-Lopez, A.; Plane, J. M. C.; Wevill, D.; Carpenter, L.; Rickard, A. R.; Monks, P. S.

2004-05-01

Renewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O'Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical. When small, those formed in the molecular iodine system swell only moderately when exposed to increased humidity environments, and swell progressively less with increasing size; this behaviour occurs whether they are formed in dry or humid environments, in contrast to those in the CH2I2 system. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed.

Armed Forces Institute of Regenerative Medicine Annual Report 2010

DTIC Science & Technology

2011-01-01

manufacture a PDO bioabsorbable stent (Figure II-12) and a fracture -resistant nitinol stent (Figure II-13). 2. Mechanically test tissue following...storage in anhy­ drous fluid (Figure II-14). 3. Conduct fatigue tests on fracture -resistant stents (Figure II-15). 4. Mechanically evaluate the...veloped a fracture -resistant tissue-lined nitinol stent, and mechanically tested both stents. Both designs performed exceptionally well in mechanical

Orange protein has a role in phytoene synthase stabilization in sweetpotato.

PubMed

Park, Seyeon; Kim, Ho Soo; Jung, Young Jun; Kim, Sun Ha; Ji, Chang Yoon; Wang, Zhi; Jeong, Jae Cheol; Lee, Haeng-Soon; Lee, Sang Yeol; Kwak, Sang-Soo

2016-09-16

Carotenoids have essential roles in light-harvesting processes and protecting the photosynthetic machinery from photo-oxidative damage. Phytoene synthase (PSY) and Orange (Or) are key plant proteins for carotenoid biosynthesis and accumulation. We previously isolated the sweetpotato (Ipomoea batatas) Or gene (IbOr), which is involved in carotenoid accumulation and salt stress tolerance. The molecular mechanism underlying IbOr regulation of carotenoid accumulation was unknown. Here, we show that IbOr has an essential role in regulating IbPSY stability via its holdase chaperone activity both in vitro and in vivo. This protection results in carotenoid accumulation and abiotic stress tolerance. IbOr transcript levels increase in sweetpotato stem, root, and calli after exposure to heat stress. IbOr is localized in the nucleus and chloroplasts, but interacts with IbPSY only in chloroplasts. After exposure to heat stress, IbOr predominantly localizes in chloroplasts. IbOr overexpression in transgenic sweetpotato and Arabidopsis conferred enhanced tolerance to heat and oxidative stress. These results indicate that IbOr holdase chaperone activity protects IbPSY stability, which leads to carotenoid accumulation, and confers enhanced heat and oxidative stress tolerance in plants. This study provides evidence that IbOr functions as a molecular chaperone, and suggests a novel mechanism regulating carotenoid accumulation and stress tolerance in plants.

Inhibition of seagrass photosynthesis by ultraviolet-B radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trocine, R.P.; Rice, J.D.; Wells, G.N.

1981-07-01

Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme (Kuetz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated. Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. Syringodium appeared to rely primarily on a thick epidermal cellmore » layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species. Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation.« less

Preventive role of lens antioxidant defense mechanism against riboflavin-mediated sunlight damaging of lens crystallins.

PubMed

Anbaraki, Afrooz; Khoshaman, Kazem; Ghasemi, Younes; Yousefi, Reza

2016-10-01

The main components of sunlight reaching the eye lens are UVA and visible light exerting their photo-damaging effects indirectly by the aid of endogenous photosensitizer molecules such as riboflavin (RF). In this study, lens proteins solutions were incubated with RF and exposed to the sunlight. Then, gel mobility shift analysis and different spectroscopic assessments were applied to examine the structural damaging effects of solar radiation on these proteins. Exposure of lens proteins to direct sunlight, in the presence of RF, leads to marked structural crosslinking, oligomerization and proteolytic instability. These structural damages were also accompanied with reduction in the emission fluorescence of Trp and Tyr and appearance of a new absorption peak between 300 and 400nm which can be related to formation of new chromophores. Also, photo-oxidation of lens crystallins increases their oligomeric size distribution as examined by dynamic light scattering analysis. The above mentioned structural insults, as potential sources of sunlight-induced senile cataract and blindness, were significantly attenuated in the presence of ascorbic acid and glutathione which are two important components of lens antioxidant defense system. Therefore, the powerful antioxidant defense mechanism of eye lens is an important barrier against molecular photo-damaging effects of solar radiations during the life span. Copyright © 2016 Elsevier B.V. All rights reserved.

Responses of tree species to heat waves and extreme heat events.

PubMed

Teskey, Robert; Wertin, Timothy; Bauweraerts, Ingvar; Ameye, Maarten; McGuire, Mary Anne; Steppe, Kathy

2015-09-01

The number and intensity of heat waves has increased, and this trend is likely to continue throughout the 21st century. Often, heat waves are accompanied by drought conditions. It is projected that the global land area experiencing heat waves will double by 2020, and quadruple by 2040. Extreme heat events can impact a wide variety of tree functions. At the leaf level, photosynthesis is reduced, photooxidative stress increases, leaves abscise and the growth rate of remaining leaves decreases. In some species, stomatal conductance increases at high temperatures, which may be a mechanism for leaf cooling. At the whole plant level, heat stress can decrease growth and shift biomass allocation. When drought stress accompanies heat waves, the negative effects of heat stress are exacerbated and can lead to tree mortality. However, some species exhibit remarkable tolerance to thermal stress. Responses include changes that minimize stress on photosynthesis and reductions in dark respiration. Although there have been few studies to date, there is evidence of within-species genetic variation in thermal tolerance, which could be important to exploit in production forestry systems. Understanding the mechanisms of differing tree responses to extreme temperature events may be critically important for understanding how tree species will be affected by climate change. © 2014 John Wiley & Sons Ltd.

Excited triplet states as photooxidants in surface waters

NASA Astrophysics Data System (ADS)

Canonica, S.

2012-12-01

The chromophoric components of dissolved organic matter (DOM) are generally the main absorbers of sunlight in surface waters and therefore a source of transient reactants under irradiation. Such short-lived species can be relevant for the fate of various classes of chemical contaminants in the aquatic environment. The present contribution focuses on the role of excited triplet states of chromophoric DOM, 3CDOM*, as transient photooxidants initiating the transformation and degradation of organic chemical contaminants. An early study [1] indicated that 3CDOM* may play a dominant role in the photo-induced transformation of electron-rich phenols, a conclusion which was later fortified by the results of transient absorption investigations using aromatic ketones as model photosensitizers [2] and by a recent careful analysis of the effect of oxygen concentration on transformation rates [3]. The variety of aquatic contaminants shown to be affected by triplet-induced oxidation has kept increasing, phenylurea herbicides [4], sulfonamide antibiotics [5] and some phytoestrogens [6] being prominent examples. Recent research has shown that the triplet-induced transformation of specific contaminants, especially aromatic nitrogen compounds, could be inhibited by the presence of DOM, very probably due to its antioxidant moieties [7]. While such moieties are not relevant for the quenching of 3CDOM*, they are expected to react with it in a similar way as the studied contaminants. Analogous reactions can be postulated to occur in liquid or solid phases of the atmospheric environment, as demonstrated in the case of HONO formation [8]. References 1. Canonica, S.; Jans, U.; Stemmler, K.; Hoigné, J. Transformation kinetics of phenols in water: Photosensitization by dissolved natural organic material and aromatic ketones. Environ. Sci. Technol. 1995, 29 (7), 1822-1831. 2. Canonica, S.; Hellrung, B.; Wirz, J. Oxidation of phenols by triplet aromatic ketones in aqueous solution. J. Phys. Chem. A 2000, 104 (6), 1226-1232. 3. Golanoski, K. S.; Fang, S.; Del Vecchio, R.; Blough, N. V. Investigating the mechanism of phenol photooxidation by humic substances. Environ. Sci. Technol. 2012, 46 (7), 3912-3920. 4. Gerecke, A. C.; Canonica, S.; Müller, S. R.; Schärer, M.; Schwarzenbach, R. P. Quantification of dissolved natural organic matter (DOM) mediated phototransformation of phenylurea herbicides in lakes. Environ. Sci. Technol. 2001, 35 (19), 3915-3923. 5. Boreen, A. L.; Arnold, W. A.; McNeill, K. Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: Identification of an SO2 extrusion photoproduct. Environ. Sci. Technol. 2005, 39 (10), 3630-3638. 6. Felcyn, J. R.; Davis, J. C. C.; Tran, L. H.; Berude, J. C.; Latch, D. E. Aquatic photochemistry of isoflavone phytoestrogens: Degradation kinetics and pathways. Environ. Sci. Technol. 2012, 46 (12), 6698-6704. 7. Wenk, J.; Canonica, S. Phenolic antioxidants inhibit the triplet-induced transformation of anilines and sulfonamide antibiotics in aqueous solution. Environ. Sci. Technol. 2012, 46 (10), 5455-5462. 8. George, C.; Strekowski, R. S.; Kleffmann, J.; Stemmler, K.; Ammann, M. Photoenhanced uptake of gaseous NO2 on solid-organic compounds: a photochemical source of HONO? Faraday Discuss. 2005, 130, 195-210.

An intrinsically disordered photosystem II subunit, PsbO, provides a structural template and a sensor of the hydrogen-bonding network in photosynthetic water oxidation.

PubMed

Offenbacher, Adam R; Polander, Brandon C; Barry, Bridgette A

2013-10-04

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global (13)C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster.

A Miniature Bioassay for Testing the Acute Phytotoxicity of Photosystem II Herbicides on Seagrass

PubMed Central

Wilkinson, Adam D.; Collier, Catherine J.; Flores, Florita; Mercurio, Phil; O’Brien, Jake; Ralph, Peter J.; Negri, Andrew P.

2015-01-01

Photosystem II (PSII) herbicides have been detected in nearshore tropical waters such as those of the Great Barrier Reef and may add to the pressure posed by runoff containing sediments and nutrients to threatened seagrass habitats. There is a growing number of studies into the potential effects of herbicides on seagrass, generally using large experimental setups with potted plants. Here we describe the successful development of an acute 12-well plate phytotoxicity assay for the PSII herbicide Diuron using isolated Halophila ovalis leaves. Fluorescence images demonstrated Diuron affected the entire leaf surface evenly and responses were not influenced by isolating leaves from the plant. The optimum exposure duration was 24 h, by which time the inhibition of effective quantum yield of PSII (∆F/Fm’) was highest and no deterioration of photosystems was evident in control leaves. The inhibition of ∆F/Fm’ by Diuron in isolated H. ovalis leaves was identical to both potted and hydroponically grown plants (with leaves remaining attached to rhizomes), indicating similar reductions in photosynthetic activity in these acute well-plate assays. The sensitivity of the assay was not influenced by irradiance (range tested 40 to 400 μmol photons m-2 s-1). High irradiance, however, caused photo-oxidative stress in H. ovalis and this generally impacted in an additive or sub-additive way with Diuron to damage PSII. The bioassay using isolated leaves is more rapid, uses far less biological material and does not rely on specialised aquarium facilities in comparison with assays using potted plants. The development and validation of this sensitive bioassay will be useful to reliably screen and monitor the phytotoxicity of existing and emerging PSII herbicides and contribute to risk assessments and water quality guideline development in the future. PMID:25674791

Inactivation and deficiency of core proteins of photosystems I and II caused by genetical phylloquinone and plastoquinone deficiency but retained lamellar structure in a T-DNA mutant of Arabidopsis.

PubMed

Shimada, Hiroshi; Ohno, Ryoichi; Shibata, Masaru; Ikegami, Isamu; Onai, Kiyoshi; Ohto, Masa-aki; Takamiya, Ken-ichiro

2005-02-01

Phylloquinone, a substituted 1,4-naphthoquinone with an 18-carbon-saturated phytyl tail, functions as a bound one-electron carrier cofactor at the A1 site of photosystem I (PSI). A Feldmann tag line mutant, no. 2755 (designated as abc4 hereafter), showed pale-green young leaves and white old leaves. The mutated nuclear gene encoded 1,4-dihydroxy-2-naphtoic acid phytyltransferase, an enzyme of phylloquinone biosynthesis, and high-performance liquid chromatography analysis revealed that the abc4 mutant contained no phylloquinone, and only about 3% plastoquinone. Photooxidation of P700 of PSI in the abc4 mutant was not observed, and reduced-versus-oxidized difference spectroscopy indicated that the abc4 mutant had no P700. The maximum quantum yield of photosystem II (PSII) in the abc4 mutant was much decreased, and the electron transfer from PSII to PSI in the abc4 mutant did not occur. For the pale-green leaves of the abc4 mutant plant, the ultrastructure of the chloroplasts was almost the same as that of the wild-type plant. However, the chloroplasts in the albino leaves of the mutant were smaller and had a lot of grana thylakoids and few stroma thylakoids. The amounts of PSI and PSII core subunits in the abc4 mutant were significantly decreased compared with those in the wild type. These results suggested that a deficiency of phylloquinone in PSI caused the abolishment of PSI and a partial defect of PSII due to a significant decrease of plastoquinone, but did not influence the ultrastructure of the chloroplasts in young leaves.

Singlet oxygen sensitizing materials based on porous silicone: photochemical characterization, effect of dye reloading and application to water disinfection with solar reactors.

PubMed

Manjón, Francisco; Santana-Magaña, Montserrat; García-Fresnadillo, David; Orellana, Guillermo

2010-06-01

Photogeneration of singlet molecular oxygen ((1)O(2)) is applied to organic synthesis (photooxidations), atmosphere/water treatment (disinfection), antibiofouling materials and in photodynamic therapy of cancer. In this paper, (1)O(2) photosensitizing materials containing the dyes tris(4,4'-diphenyl-2,2'-bipyridine)ruthenium(II) (1, RDB(2+)) or tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) (2, RDP(2+)), immobilized on porous silicone (abbreviated RDB/pSil and RDP/pSil), have been produced and tested for waterborne Enterococcus faecalis inactivation using a laboratory solar simulator and a compound parabolic collector (CPC)-based solar photoreactor. In order to investigate the feasibility of its reuse, the sunlight-exposed RDP/pSil sensitizing material (RDP/pSil-a) has been reloaded with RDP(2+) (RDP/pSil-r). Surprisingly, results for bacteria inactivation with the reloaded material have demonstrated a 4-fold higher efficiency compared to those of either RDP/pSil-a, unused RDB/pSil and the original RDP/pSil. Surface and bulk photochemical characterization of the new material (RDP/pSil-r) has shown that the bactericidal efficiency enhancement is due to aggregation of the silicone-supported photosensitizer on the surface of the polymer, as evidenced by confocal fluorescence lifetime imaging microscopy (FLIM). Photogenerated (1)O(2) lifetimes in the wet sensitizer-doped silicone have been determined to be ten times longer than in water. These facts, together with the water rheology in the solar reactor and the interfacial production of the biocidal species, account for the more effective disinfection observed with the reloaded photosensitizing material. These results extend and improve the operational lifetime of photocatalytic materials for point-of-use (1)O(2)-mediated solar water disinfection.

Zeaxanthin Protects Plant Photosynthesis by Modulating Chlorophyll Triplet Yield in Specific Light-harvesting Antenna Subunits*

PubMed Central

Dall'Osto, Luca; Holt, Nancy E.; Kaligotla, Shanti; Fuciman, Marcel; Cazzaniga, Stefano; Carbonera, Donatella; Frank, Harry A.; Alric, Jean; Bassi, Roberto

2012-01-01

Plants are particularly prone to photo-oxidative damage caused by excess light. Photoprotection is essential for photosynthesis to proceed in oxygenic environments either by scavenging harmful reactive intermediates or preventing their accumulation to avoid photoinhibition. Carotenoids play a key role in protecting photosynthesis from the toxic effect of over-excitation; under excess light conditions, plants accumulate a specific carotenoid, zeaxanthin, that was shown to increase photoprotection. In this work we genetically dissected different components of zeaxanthin-dependent photoprotection. By using time-resolved differential spectroscopy in vivo, we identified a zeaxanthin-dependent optical signal characterized by a red shift in the carotenoid peak of the triplet-minus-singlet spectrum of leaves and pigment-binding proteins. By fractionating thylakoids into their component pigment binding complexes, the signal was found to originate from the monomeric Lhcb4–6 antenna components of Photosystem II and the Lhca1–4 subunits of Photosystem I. By analyzing mutants based on their sensitivity to excess light, the red-shifted triplet-minus-singlet signal was tightly correlated with photoprotection in the chloroplasts, suggesting the signal implies an increased efficiency of zeaxanthin in controlling chlorophyll triplet formation. Fluorescence-detected magnetic resonance analysis showed a decrease in the amplitude of signals assigned to chlorophyll triplets belonging to the monomeric antenna complexes of Photosystem II upon zeaxanthin binding; however, the amplitude of carotenoid triplet signal does not increase correspondingly. Results show that the high light-induced binding of zeaxanthin to specific proteins plays a major role in enhancing photoprotection by modulating the yield of potentially dangerous chlorophyll-excited states in vivo and preventing the production of singlet oxygen. PMID:23066020

Effect of nitrogen oxides (NO and NO2) and toluene on SO2 photooxidation, nucleation and growth: A smog chamber study

NASA Astrophysics Data System (ADS)

Li, Kangwei; Chen, Linghong; White, Stephen J.; Han, Ke; Lv, Biao; Bao, Kaiji; Wu, Xuecheng; Gao, Xiang; Azzi, Merched; Cen, Kefa

2017-08-01

The formation and growth of new particles has recently been shown to have a significant influence on Chinese haze pollution, and sulfuric acid has long been recognized as a major contributor to new particle formation. In this study, four comparison groups of experiments related to SO2 photooxidation, as well as aerosol nucleation and growth, have been conducted in the CAPS-ZJU (Complex Air Pollution Study-Zhejiang University) smog chamber. These were conducted either under SO2/NOx or SO2/toluene gas-phase environments in the absence of seed particles. During aerosol nucleation and growth process, several physical properties such as mass, size and effective density were measured simultaneously by Scanning Mobility Particle Sizer (SMPS) and Differential Mobility Analyzer-Aerosol Particle Mass Analyzer-Condensation Particle Counter (DMA-APM-CPC). The effective density of new particles decreased from 1.8 to 1.35 g/cm3 as the particle size increased from 20 to 65 nm. The single particle mass showed good power-law relationship with mobility diameter, with an average mass-mobility exponent of 2.885. A new algorithm and a reference density of 1.38 g/cm3 based on size-resolved single particle mass (SPM) were proposed to calculate the mass concentration of new particles. Two methods based on Log Normal and Max Concentration were applied to derive particle growth rate (GR), and data merging from both methods was implemented to decrease calculation uncertainty. Meanwhile, both continuous nucleation and inhibition of further growth in sub-20 nm size range were observed in different experiments depending on composition, and possible reasons were analyzed. The presence of NO was found to suppress nucleation and subsequent aerosol growth; while the presence of NO2 or toluene promoted it. It was concluded that decreasing NOx (NO or NO2) or increasing toluene may promote SO2 photooxidation, nucleation and subsequent aerosol growth, all of which is significant for deeper understanding of complex air pollution in China.

Assessing the influence of NOx concentrations and relative humidity on secondary organic aerosol yields from α-pinene photo-oxidation through smog chamber experiments and modelling calculations

NASA Astrophysics Data System (ADS)

Stirnweis, Lisa; Marcolli, Claudia; Dommen, Josef; Barmet, Peter; Frege, Carla; Platt, Stephen M.; Bruns, Emily A.; Krapf, Manuel; Slowik, Jay G.; Wolf, Robert; Prévôt, Andre S. H.; Baltensperger, Urs; El-Haddad, Imad

2017-04-01

Secondary organic aerosol (SOA) yields from the photo-oxidation of α-pinene were investigated in smog chamber (SC) experiments at low (23-29 %) and high (60-69 %) relative humidity (RH), various NOx / VOC ratios (0.04-3.8) and with different aerosol seed chemical compositions (acidic to neutralized sulfate-containing or hydrophobic organic). A combination of a scanning mobility particle sizer and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer was used to determine SOA mass concentration and chemical composition. We used a Monte Carlo approach to parameterize smog chamber SOA yields as a function of the condensed phase absorptive mass, which includes the sum of OA and the corresponding bound liquid water content. High RH increased SOA yields by up to 6 times (1.5-6.4) compared to low RH. The yields at low NOx / VOC ratios were in general higher compared to yields at high NOx / VOC ratios. This NOx dependence follows the same trend as seen in previous studies for α-pinene SOA. A novel approach of data evaluation using volatility distributions derived from experimental data served as the basis for thermodynamic phase partitioning calculations of model mixtures in this study. These calculations predict liquid-liquid phase separation into organic-rich and electrolyte phases. At low NOx conditions, equilibrium partitioning between the gas and liquid phases can explain most of the increase in SOA yields observed at high RH, when in addition to the α-pinene photo-oxidation products described in the literature, fragmentation products are added to the model mixtures. This increase is driven by both the increase in the absorptive mass and the solution non-ideality described by the compounds' activity coefficients. In contrast, at high NOx, equilibrium partitioning alone could not explain the strong increase in the yields with RH. This suggests that other processes, e.g. reactive uptake of semi-volatile species into the liquid phase, may occur and be enhanced at higher RH, especially for compounds formed under high NOx conditions, e.g. carbonyls.

Improving the Photo-Oxidative Performance of Bi2MoO6 by Harnessing the Synergy between Spatial Charge Separation and Rational Co-Catalyst Deposition.

PubMed

Wu, Xuelian; Hart, Judy N; Wen, Xiaoming; Wang, Liang; Du, Yi; Dou, Shi Xue; Ng, Yun Hau; Amal, Rose; Scott, Jason

2018-03-21

It has been reported that photogenerated electrons and holes can be directed toward specific crystal facets of a semiconductor particle, which is believed to arise from the differences in their surface electronic structures, suggesting that different facets can act as either photoreduction or photo-oxidation sites. This study examines the propensity for this effect to occur in faceted, plate-like bismuth molybdate (Bi 2 MoO 6 ), which is a useful photocatalyst for water oxidation. Photoexcited electrons and holes are shown to be spatially separated toward the {100} and {001}/{010} facets of Bi 2 MoO 6 , respectively, by facet-dependent photodeposition of noble metals (Pt, Au, and Ag) and metal oxides (PbO 2 , MnO x , and CoO x ). Theoretical calculations revealed that differences in energy levels between the conduction bands and valence bands of the {100} and {001}/{010} facets can contribute to electrons and holes being drawn to different surfaces of the plate-like Bi 2 MoO 6 . Utilizing this knowledge, the photo-oxidative capability of Bi 2 MoO 6 was improved by adding an efficient water oxidation co-catalyst, CoO x , to the system, whereby the extent of enhancement was shown to be governed by the co-catalyst location. A greater oxygen evolution occurred when CoO x was selectively deposited on the hole-rich {001}/{010} facets of Bi 2 MoO 6 compared to when CoO x was randomly located across all of the facets. The elevated performance exhibited for the selectively loaded CoO x /Bi 2 MoO 6 was ascribed to the greater opportunity for hole trapping by the co-catalyst being accentuated over other potentially detrimental effects, such as the co-catalyst acting as a recombination medium and/or covering reactive sites. The results indicate that harnessing the synergy between the spatial charge separation and the co-catalyst location on the appropriate facets of plate-like Bi 2 MoO 6 can promote its photocatalytic activity.

Redox Signaling and CBF-Responsive Pathway Are Involved in Salicylic Acid-Improved Photosynthesis and Growth under Chilling Stress in Watermelon

PubMed Central

Cheng, Fei; Lu, Junyang; Gao, Min; Shi, Kai; Kong, Qiusheng; Huang, Yuan; Bie, Zhilong

2016-01-01

Salicylic acid (SA) plays an important role in plant response to abiotic stresses. This study investigated the potential role of SA in alleviating the adverse effects of chilling stress on photosynthesis and growth in watermelon (Citrullus lanatus). Chilling stress induced the simultaneous accumulation of free and conjugated SA in watermelon plants, and the chilling-induced SA production was attributed to the phenylalanine ammonia-lyase pathway. Applying SA at moderate concentrations induced chilling tolerance, whereas inhibition of SA biosynthesis by L-α-aminooxy-β-phenylpropionic acid (AOPP) increased the photooxidation of PS II under chilling stress in watermelon, resulting in reduced photosynthesis and growth. Chilling induced a transient increase in the ratios of reduced to oxidized glutathione and reduced ascorbate to dehydroascorbate. Then, the expression of antioxidant genes was upregulated, and the activities of antioxidant enzymes were enhanced. Furthermore, SA-induced chilling tolerance was associated with cellular glutathione and ascorbate homeostasis, which served as redox signals to regulate antioxidant metabolism under chilling stress. AOPP treatment stimulated the chilling-induced expression of cold-responsive genes, particularly via C-repeat binding factors CBF3 and CBF4. These results confirm the synergistic role of SA signaling and the CBF-dependent responsive pathway during chilling stress in watermelon. PMID:27777580

30 CFR 57.22201 - Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). 57.22201 Section 57.22201 Mineral Resources MINE SAFETY AND HEALTH....22201 Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). All mines shall...

30 CFR 57.22201 - Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). 57.22201 Section 57.22201 Mineral Resources MINE SAFETY AND HEALTH....22201 Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). All mines shall...

Inhibition of seagrass photosynthesis by ultraviolet-B radiation.

PubMed

Trocine, R P; Rice, J D; Wells, G N

1981-07-01

Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme Kütz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated.Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. This mechanism effectively attenuated photosynthetic inhibition induced by ultraviolet-B dose rates and dosages in excess of natural conditions. Syringodium appeared to rely primarily on a thick epidermal cell layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species.Observations obtained in this study seem to suggest the possibility of anthocyanin and/or other flavonoid synthesis as an adaptation to long term ultraviolet-B irradiation by these species. In addition, Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation.

Mechanical and thermal stability of molecularly engineered copper-silica interfaces using organosilane nanolayers

NASA Astrophysics Data System (ADS)

Gandhi, Darshan Dinesh

Future generation silicon integrated circuits requires new materials with low dielectric permittivity kappa < 2.0 and ultra-thin barrier layers (e.g., <3 nm) to create high-reliability, high-performance wiring. Preserving the structural and functional integrity of interfaces is a crucial aspect of realizing reliable integrated circuits with nanodevice components. Molecular nanolayers (MNLs) provide the unique ability to tailor interface properties by adjusting molecular termini, layering, branching or length, thereby making them attractive alternatives to conventional barrier materials. Developing a fundamental understanding of the stability and properties of MNLs at thin film interfaces, and their correlation with parameters such as terminal group chemistries molecular length and surface coverage are key to utilizing them in nanodevice applications. This work addresses some of the key challenges pertaining to modifying Cu-silica interfaces with MNLs with appropriate terminal groups. The resultant effects on, and the inter-relationships between, the chemical, mechanical and electrical properties are investigated. Modifying Cu-silica interface with MNLs results in increased Cu diffusioninduced time-to-failure when subject to electrothermal stresses. The extent of enhancement depends on the terminal chemistry of the MNLs interacting with the overlying Cu. Upon annealing, it is found that MNLs form strong covalent linkages at both Cu-MNL and MNL-silica interfaces resulting in unprecedented values of interface toughness, values exceeding 20 Jm-2. Although strong bonding at Cu-MNL and MNL-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte MNL bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. Exposing MNLs to UV light, results in photo-oxidation of the terminal mercaptan groups. These photo-oxidized termini form strong complexes with Cu that results in enhancement by a factor-of-10 in device failure times. Using a combination of UV-exposure prior to Cu metallization and annealing after Cu metallization should result in enhanced device failure times and interface toughness, resulting in chemically isolated and mechanically strong interfaces. This work also shows that passivating Cu surfaces with MNLs can decrease surface leakage currents due to curtailed in-plane Cu transport (low voltages). Formation of strong complexes with Cu can immobilize Cu and reduce the leakage currents and result in higher breakdown voltages. Moreover, the strategy of using MNLs can be applied to passivate pore surfaces in mesoporous silica (MPS) films to suppress water uptake and Cu penetration. The molecularly passivated dielectrics (S-MPS) exhibit 50% lower fracture toughness than unfunctionalized films, and fracture closer to the Cu/S-MPS interface. Electron spectroscopy analyses show that the fracture pathway is governed by the Cu penetration depth into the MPS. Our results show that molecular passivation of porous films not only inhibit metal penetration and water uptake, but also can be used to tune the fracture pathway. The results from this thesis are of importance for harnessing MNLs for the use in future device wiring applications.

The Role of Electronically Excited States and Free Radicals in Ultraviolet-Induced Lens Opacification.

DTIC Science & Technology

1980-12-01

Triplet State in UV-Induced Cataractogenesis ................................................. 63 D. Possible Role of a Photo-Oxidation Product of the...12,13). Some of the pigments have been isolated and identified as glucosides of hydroxy kynurenine and other oxidation products of tryptophan (14...dependence of UV-induced free-radical production , sought to identify the excited states and free radicals in the lens, studied the kinet- ics of free

Laser-induced fabrication of nanoporous monolayer WS2 membranes

NASA Astrophysics Data System (ADS)

Danda, Gopinath; Masih Das, Paul; Drndić, Marija

2018-07-01

Porous transition metal dichalcogenides (TMDs) are promising candidates for a variety of catalytic, purification, and energy storage applications. Despite recent advances, current fabrication techniques face issues concerning scalability and control over sample porosity. By utilizing water-assisted laser irradiation, we present here a new method for the fabrication of micron-scale, atomically-thin nanoporous tungsten disulfide (WS2) membranes. The electronic and physical structures of the porous membranes are characterized with photoluminescence (PL) spectroscopy and aberration-corrected scanning transmission electron microscopy (AC-STEM), respectively. With increasing laser irradiation dose, we observe a decay of PL signal, and a relative increase in the trion contribution compared to that of the neutral exciton, suggesting defect-related n-type doping and degradation of the membrane. AC-STEM images show the nucleation of tungsten oxide islands on the membrane, and the formation of triangular defect clusters containing a combination of nanopores and oxide-filled regions, providing insight at the atomic level into the photo-oxidation process in TMDs. A linear dependence of the nanoporous area percentage on the laser irradiation dose over the range of 102–105 W cm‑2 is observed. The methods proposed here pave the way for the scalable production of nanoporous membranes through the laser-induced photo-oxidation of WS2 and other transition metal dichalcogenides.

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

NASA Astrophysics Data System (ADS)

Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

Diverse strategies of O2 usage for preventing photo-oxidative damage under CO2 limitation during algal photosynthesis.

PubMed

Shimakawa, Ginga; Matsuda, Yusuke; Nakajima, Kensuke; Tamoi, Masahiro; Shigeoka, Shigeru; Miyake, Chikahiro

2017-01-20

Photosynthesis produces chemical energy from photon energy in the photosynthetic electron transport and assimilates CO 2 using the chemical energy. Thus, CO 2 limitation causes an accumulation of excess energy, resulting in reactive oxygen species (ROS) which can cause oxidative damage to cells. O 2 can be used as an alternative energy sink when oxygenic phototrophs are exposed to high light. Here, we examined the responses to CO 2 limitation and O 2 dependency of two secondary algae, Euglena gracilis and Phaeodactylum tricornutum. In E. gracilis, approximately half of the relative electron transport rate (ETR) of CO 2 -saturated photosynthesis was maintained and was uncoupled from photosynthesis under CO 2 limitation. The ETR showed biphasic dependencies on O 2 at high and low O 2 concentrations. Conversely, in P. tricornutum, most relative ETR decreased in parallel with the photosynthetic O 2 evolution rate in response to CO 2 limitation. Instead, non-photochemical quenching was strongly activated under CO 2 limitation in P. tricornutum. The results indicate that these secondary algae adopt different strategies to acclimatize to CO 2 limitation, and that both strategies differ from those utilized by cyanobacteria and green algae. We summarize the diversity of strategies for prevention of photo-oxidative damage under CO 2 limitation in cyanobacterial and algal photosynthesis.

Impact of Lipid and Protein Co-oxidation on Digestibility of Dairy Proteins in Oil-in-Water (O/W) Emulsions.

PubMed

Obando, Mónica; Papastergiadis, Antonios; Li, Shanshan; De Meulenaer, Bruno

2015-11-11

Enrichment of polyunsaturated fatty acids (PUFAs) is a growing trend in the food industry. However, PUFAs are known to be susceptible to lipid oxidation. It has been shown that oxidizing lipids react with proteins present in the food and that as a result polymeric protein complexes are produced. Therefore, the aim of this work was to investigate the impact of lipid and protein co-oxidation on protein digestibility. Casein and whey protein (6 mg/mL) based emulsions with 1% oil with different levels of PUFAs were subjected to respectively autoxidation and photo-oxidation. Upon autoxidation at 70 °C, protein digestibility of whey protein based emulsions containing fish oil decreased to 47.7 ± 0.8% after 48 h, whereas in the controls without oil 67.8 ± 0.7% was observed. Upon photo-oxidation at 4 °C during 30 days, mainly casein-based emulsions containing fish oil were affected: the digestibility amounted to 43.9 ± 1.2%, whereas in the control casein solutions without oil, 72.6 ± 0.2% of the proteins were digestible. Emulsions containing oils with high PUFA levels were more prone to lipid oxidation and thus upon progressive oxidation showed a higher impact on protein digestibility.

Long-term Simulation of Photo-oxidants and Particulate Matter Over Europe With The Eurad Modeling System

NASA Astrophysics Data System (ADS)

Memmesheimer, M.; Friese, E.; Jakobs, H. J.; Feldmann, H.; Ebel, A.; Kerschgens, M. J.

During recent years the interest in long-term applications of air pollution modeling systems (AQMS) has strongly increased. Most of these models have been developed for the application to photo-oxidant episodes during the last decade. In this contribu- tion a long-term application of the EURAD modeling sytem to the year 1997 is pre- sented. Atmospheric particles are included using the Modal Aerosol Dynamics Model for Europe (MADE). Meteorological fields are simulated by the mesoscale meteoro- logical model MM5, gas-phase chemistry has been treated with the RACM mecha- nism. The nesting option is used to zoom in areas of specific interest. Horizontal grid sizes are 125 km for the reginal scale, and 5 km for the local scale covering the area of North-Rhine-Westfalia (NRW). The results have been compared to observations of the air quality network of the environmental agency of NRW for the year 1997. The model results have been evaluated using the data quality objectives of the EU direc- tive 99/30. Further improvement for application of regional-scale air quality models is needed with respect to emission data bases, coupling to global models to improve the boundary values, interaction between aerosols and clouds and multiphase modeling.

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia.

PubMed

Liu, Yingjun; Seco, Roger; Kim, Saewung; Guenther, Alex B; Goldstein, Allen H; Keutsch, Frank N; Springston, Stephen R; Watson, Thomas B; Artaxo, Paulo; Souza, Rodrigo A F; McKinney, Karena A; Martin, Scot T

2018-04-01

Nitrogen oxides (NO x ) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning. The afternoon concentrations of reactive nitrogen oxides (NO y ), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3 . The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.

A novel high light-inducible carotenoid-binding protein complex in the thylakoid membranes of Synechocystis PCC 6803

PubMed Central

Daddy, Soumana; Zhan, Jiao; Jantaro, Saowarath; He, Chenliu; He, Qingfang; Wang, Qiang

2015-01-01

Synechocystis sp. PCC 6803 is a model cyanobacterium extensively used to study photosynthesis. Here we reveal a novel high light-inducible carotenoid-binding protein complex (HLCC) in the thylakoid membranes of Synechocystis PCC 6803 cells exposed to high intensity light. Zeaxanthin and myxoxanthophyll accounted for 29.8% and 54.8%, respectively, of the carotenoids bound to the complex. Using Blue-Native PAGE followed by 2D SDS-PAGE and mass spectrometry, we showed that the HLCC consisted of Slr1128, IsiA, PsaD, and HliA/B. We confirmed these findings by SEAD fluorescence cross-linking and anti-PsaD immuno-coprecipitation analyses. The expression of genes encoding the protein components of the HLCC was enhanced by high light illumination and artificial oxidative stress. Deletion of these proteins resulted in impaired state transition and increased sensitivity to oxidative and/or high light stress, as indicated by increased membrane peroxidation. Therefore, the HLCC protects thylakoid membranes from extensive photooxidative damage, likely via a mechanism involving state transition. PMID:25820628

Immobilization of kojic acid in ZnAl-hydrotalcite like compounds

NASA Astrophysics Data System (ADS)

Ambrogi, Valeria; Perioli, Luana; Nocchetti, Morena; Latterini, Loredana; Pagano, Cinzia; Massetti, Elena; Rossi, Carlo

2012-01-01

Kojic acid (KOJ) is a melanin synthesis inhibitor widely used as skin lightening agent in topical preparations. Unfortunately it is easily susceptible to photo-oxidation, phenomenon responsible for chemical and organoleptic modifications. The aim of this work was the intercalation of KOJ in hydrotalcite-like compounds (HTlc) in order to stabilize KOJ and to reduce its photolability. Hydrotalcite containing Zn and Al (ZnAl-HTlc) was used as host to obtain the final compound ZnAl-HTlc-KOJ. The intercalation was carried out, after many attempts, by ionic exchange mechanism by means of the strong base EtO- in anhydrous ethanol/dimethylsulfoxide (DMSO) mixture as solvent in order to generate KOJ- anions. The final product was characterized by the X-ray powder diffraction (XRPD), FT-IR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and elemental analysis. The intercalated compound was formulated in a siliconic water free self-emulsifying ointment and the in vitro release profile was evaluated. All samples (intercalation compound and its formulation) were submitted also to spectrophotometric assays in order to evaluate the matrix protective effect towards ultraviolet rays.

UV laser-induced cross-linking in peptides

PubMed Central

Leo, Gabriella; Altucci, Carlo; Bourgoin-Voillard, Sandrine; Gravagnuolo, Alfredo M.; Esposito, Rosario; Marino, Gennaro; Costello, Catherine E.; Velotta, Raffaele; Birolo, Leila

2013-01-01

RATIONALE The aim of this study was to demonstrate, and to characterize by high resolution mass spectrometry, that it is possible to preferentially induce covalent cross-links in peptides by using high energy femtosecond UV laser pulses. The cross-link is readily formed only when aromatic amino acids are present in the peptide sequence. METHODS Three peptides, xenopsin, angiotensin I, interleukin, individually or in combination, were exposed to high energy femtosecond UV laser pulses, either alone or in the presence of spin trapping molecules, the reaction products being characterized by high resolution mass spectrometry. RESULTS High resolution mass spectrometry and spin trapping strategies showed that cross-linking occurs readily, proceeds via a radical mechanism, and is the highly dominant reaction, proceeding without causing significant photo-damage in the investigated range of experimental parameters. CONCLUSIONS High energy femtosecond UV laser pulses can be used to induce covalent cross-links between aromatic amino acids in peptides, overcoming photo-oxidation processes, that predominate as the mean laser pulse intensity approaches illumination conditions achievable with conventional UV light sources. PMID:23754800

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens.

PubMed

Monteagudo, J M; Durán, A; Guerra, J; García-Peña, F; Coca, P

2008-03-01

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.

Chiral Templating of Self-Assembling Nanostructures by Circularly Polarized Light

PubMed Central

Yeom, Jihyeon; Yeom, Bongjun; Chan, Henry; Smith, Kyle W.; Dominguez-Medina, Sergio; Bahng, Joong Hwan; Zhao, Gongpu; Chang, Wei-Shun; Chang, Sung Jin; Chuvilin, Andrey; Melnikau, Dzmitry; Rogach, Andrey L.; Zhang, Peijun; Link, Stephan; Král, Petr; Kotov, Nicholas A.

2015-01-01

Chemical reactions affected by spin angular momenta of circularly polarized photons are rare and display low enantiomeric excess. High optical and chemical activity of nanoparticles (NPs) should facilitate the transfer of spin angular momenta of photons to nanoscale materials but such processes are unknown. Here we demonstrate that circularly polarized light (CPL) strongly affects self-assembly of racemic CdTe NPs. Illumination of NP dispersions with right- and left-handed CPL induces the formation of right- and left-handed twisted nanoribbons, respectively. Enantiomeric excess of such reactions exceeds 30% which is ~10 times higher than other CPL-induced reactions. Illumination with linearly polarized light and assembly in the dark led to straight nanoribbons. The mechanism of “templation” of NP assemblies by CPL is associated with selective photoactivation of chiral NPs and clusters followed by their photooxidation. Chiral anisotropy of interactions translates into chirality of the assembled ribbons. The ability of NPs to retain polarization information, or the “imprint” of incident photons opens new pathways for the synthesis of chiral photonic materials and allows for better understanding of the origins of biomolecular homochirality. PMID:25401922

A novel high light-inducible carotenoid-binding protein complex in the thylakoid membranes of Synechocystis PCC 6803.

PubMed

Daddy, Soumana; Zhan, Jiao; Jantaro, Saowarath; He, Chenliu; He, Qingfang; Wang, Qiang

2015-03-30

Synechocystis sp. PCC 6803 is a model cyanobacterium extensively used to study photosynthesis. Here we reveal a novel high light-inducible carotenoid-binding protein complex (HLCC) in the thylakoid membranes of Synechocystis PCC 6803 cells exposed to high intensity light. Zeaxanthin and myxoxanthophyll accounted for 29.8% and 54.8%, respectively, of the carotenoids bound to the complex. Using Blue-Native PAGE followed by 2D SDS-PAGE and mass spectrometry, we showed that the HLCC consisted of Slr1128, IsiA, PsaD, and HliA/B. We confirmed these findings by SEAD fluorescence cross-linking and anti-PsaD immuno-coprecipitation analyses. The expression of genes encoding the protein components of the HLCC was enhanced by high light illumination and artificial oxidative stress. Deletion of these proteins resulted in impaired state transition and increased sensitivity to oxidative and/or high light stress, as indicated by increased membrane peroxidation. Therefore, the HLCC protects thylakoid membranes from extensive photooxidative damage, likely via a mechanism involving state transition.

Oligomers, organosulfates, and nitroxy organosulfates identified in rainwater

NASA Astrophysics Data System (ADS)

Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

2008-12-01

Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50 percent of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We document the presence of 552 unique compounds in the rainwater over a mass range of 50-500 Da, in four compound classes (i.e., CHO, CHOS, CHON, and CHONS). The presence of oligomers, organosulfates, nitroxy organosulfates, organic acids, and linear alkylbenzene sulfonates is reported. Some compounds detected have distinct primary sources; however, the composition of the bulk of this material suggests it is formed in the atmosphere and composed of known contributors to secondary organic aerosol. For example, eight oligomer series known to form through aqueous photooxidation of methylglyoxal and organosulfate compounds known to form from 4 precursors in smog chamber experiments were identified in the rainwater samples. The oligomers, organosulfates, and nitroxy organosulfates detected in the rainwater could all contribute to the HULIS fraction of atmospheric organic matter.

Uv-Light Stabilization Additive Package For Solar Cell Module And Laminated Glass Applications

DOEpatents

Hanoka, Jack I.; Klemchuk, Peter P.

2002-03-05

An ultraviolet light stabilization additive package is used in an encapsulant material that may be used in solar cell modules, laminated glass and a variety of other applications. The ultraviolet light stabilization additive package comprises a first hindered amine light stabilizer and a second hindered amine light stabilizer. The first hindered amine light stabilizer provides thermal oxidative stabilization, and the second hindered amine light stabilizer providing photo-oxidative stabilization.

Real-Time Prediction of Tropical Cyclone Intensity Using COAMPS-TC

DTIC Science & Technology

2012-01-01

tropospheric (UT) cloud fields (i.e., cirrus clouds) long after the initial eruption cycle from gradual particle settling and re-entrainment back into the... troposphere . Volcanic sul- fur dioxide and hydrogen sulfide vapor molecules are photo-oxidized in the LS, forming gaseous sulphuric acid, which in...concentration over the eastern United States at 1815 UTC on the 17th shown in Fig. 5(a), derived from NASA Ozone Monitoring Instrument (OMI) measurements

Near-infrared branding efficiently correlates light and electron microscopy.

PubMed

Bishop, Derron; Nikić, Ivana; Brinkoetter, Mary; Knecht, Sharmon; Potz, Stephanie; Kerschensteiner, Martin; Misgeld, Thomas

2011-06-05

The correlation of light and electron microscopy of complex tissues remains a major challenge. Here we report near-infrared branding (NIRB), which facilitates such correlation by using a pulsed, near-infrared laser to create defined fiducial marks in three dimensions in fixed tissue. As these marks are fluorescent and can be photo-oxidized to generate electron contrast, they can guide re-identification of previously imaged structures as small as dendritic spines by electron microscopy.

Does aspartate 170 of the D1 polypeptide ligate the manganese cluster in photosystem II? An EPR and ESEEM Study.

PubMed

Debus, Richard J; Aznar, Constantino; Campbell, Kristy A; Gregor, Wolfgang; Diner, Bruce A; Britt, R David

2003-09-16

Aspartate 170 of the D1 polypeptide provides part of the high-affinity binding site for the first Mn(II) ion that is photooxidized during the light-driven assembly of the (Mn)(4) cluster in photosystem II [Campbell, K. A., Force, D. A., Nixon, P. J., Dole, F., Diner, B. A., and Britt, R. D. (2000) J. Am. Chem. Soc. 122, 3754-3761]. However, despite a wealth of data on D1-Asp170 mutants accumulated over the past decade, there is no consensus about whether this residue ligates the assembled (Mn)(4) cluster. To address this issue, we have conducted an EPR and ESEEM (electron spin-echo envelope modulation) study of D1-D170H PSII particles purified from the cyanobacterium Synechocystis sp. PCC 6803. The line shapes of the S(1) and S(2) state multiline EPR signals of D1-D170H PSII particles are unchanged from those of wild-type PSII particles, and the signal amplitudes correlate approximately with the lower O(2) evolving activity of the mutant PSII particles (40-60% compared to that of the wild type). These data provide further evidence that the assembled (Mn)(4) clusters in D1-D170H cells function normally, even though the assembly of the (Mn)(4) cluster is inefficient in this mutant. In the two-pulse frequency domain ESEEM spectrum of the 9.2 GHz S(2) state multiline EPR signal of D1-D170H PSII particles, the histidyl nitrogen modulation observed at 4-5 MHz is unchanged from that of wild-type PSII particles and no significant new modulation is observed. Three scenarios are presented to explain this result. (1) D1-Asp170 ligates the assembled (Mn)(4) cluster, but the hyperfine couplings to the ligating histidyl nitrogen of D1-His170 are too large or anisotropic to be detected by ESEEM analyses conducted at 9.2 GHz. (2) D1-Asp170 ligates the assembled (Mn)(4) cluster, but D1-His170 does not. (3) D1-Asp170 does not ligate the assembled (Mn)(4) cluster.

The susceptibility of the retina to photochemical damage from visible light

PubMed Central

Hunter, Jennifer J; Morgan, Jessica I W; Merigan, William H; Sliney, David H; Sparrow, Janet R; Williams, David R

2011-01-01

The photoreceptor/RPE complex must maintain a delicate balance between maximizing the absorption of photons for vision and retinal image quality while simultaneously minimizing the risk of photodamage when exposed to bright light. We review the recent discovery of two new effects of light exposure on the photoreceptor/RPE complex in the context of current thinking about the causes of retinal phototoxicity. These effects are autofluorescence photobleaching in which exposure to bright light reduces lipofuscin autofluorescence and, at higher light levels, RPE disruption in which the pattern of autofluorescence is permanently altered following light exposure. Both effects occur following exposure to visible light at irradiances that were previously thought to be safe. Photopigment, retinoids involved in the visual cycle, and bisretinoids in lipofuscin have been implicated as possible photosensitizers for photochemical damage. The mechanism of RPE disruption may follow either of these paths. On the other hand, autofluorescence photobleaching is likely an indicator of photooxidation of lipofuscin. The permanent changes inherent in RPE disruption might require modification of the light safety standards. AF photobleaching recovers after several hours although the mechanisms by which this occurs are not yet clear. Understanding the mechanisms of phototoxicity is all the more important given the potential for increased susceptibility in the presence of ocular diseases that affect either the visual cycle and/or lipofuscin accumulation. In addition, knowledge of photochemical mechanisms can improve our understanding of some disease processes that may be influenced by light exposure, such as some forms of Leber’s congenital amaurosis, and aid in the development of new therapies. Such treatment prior to intentional light exposures, as in ophthalmic examinations or surgeries, could provide an effective preventative strategy. PMID:22085795

The production of formaldehyde and hydroxyacetone in methacrolein photooxidation: New insights into mechanism and effects of water vapor.

PubMed

Xing, Yanan; Li, Huan; Huang, Liubin; Wu, Huihui; Shen, Hengqing; Chen, Zhongming

2018-04-01

Methacrolein (MACR) is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios (0 to 4.04) and relative humidities (<3% to 80%) using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde (HCHO) were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH 3 C(CH 2 )OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NO x level, while lower at high-NO x level. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NO x level is that water vapor promotes the production of methacrolein nitrate in the reaction of HOCH 2 C(CH 3 )(OO)CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89×10 -18 cm 3 /molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor. Copyright © 2017. Published by Elsevier B.V.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

PubMed

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

An analytical approach for the non-invasive selection of consolidants in rubber artworks.

PubMed

Manfredi, Marcello; Barberis, Elettra; Rava, Antonio; Poli, Tommaso; Chiantore, Oscar; Marengo, Emilio

2016-08-01

The effectiveness of five polymeric materials for the long-term conservation and restoration of rubber artworks was evaluated by accelerated photo-oxidative degradation studies. Two different ethylene vinyl-acetate resins, generally used in industry and uncommon in conservation field, a new water-based polyurethane, and two ethylene butyl-acrylate resins were assessed for the consolidation of rubber. By monitoring their degradation along time with LED imaging coupled to statistics and Fourier transform infrared spectroscopy (FTIR), the polymeric materials with the best properties that ensure the protection and security of the artwork were identified. The degradation was performed in solar box simulating the light exposure in a museum, under controlled temperature at no more than 35 °C in order to exclude the thermal effects that could influence the ageing of polymers. The mechanical stress of the treated samples was also investigated. The spectroscopic analyses, the chromatic changes study, and the mechanical degradation were used as indicators of the consolidant stability, allowing the evaluation of the materials selected for the consolidation and conservation of rubber. The ethylene-vinyl acetate copolymers resulted the most stable and suitable for the conservation of rubber artworks. Lastly, the conservation treatment identified in this research was employed for the restoration of the contemporary artwork "Presagi di Birnam" made with bicycle inner tubes by the artist Carol Rama.

Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

PubMed

Zhao, Xiaocan; Wang, Liming

2017-05-04

Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2011-06-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM-10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

A new route for the prebiotic synthesis of nucleobases and hydantoins in water/ice solutions involving the photochemistry of acetylene.

PubMed

Menor-Salván, César; Marín-Yaseli, Margarita R

2013-05-10

The origin of nucleobases and other heterocycles is a classic question in the chemistry of the origins of life. The construction of laboratory models for the abiotic synthesis of nitrogen heterocycles in plausible natural conditions also aids the understanding and prediction of chemical species in the Solar System. Here, we report a new explanation for the origin of hydantoins, purines, and pyrimidines in eutectic water/ice/urea solutions driven by ultraviolet irradiation (in the 185-254 nm range, UVC) of acetylene under anoxic conditions. An analysis of the products indicates the synthesis of hydantoin and 5-hydroxyhydantoin, the purines uric acid, xanthine, and guanine, and the pyrimidines uracil and cytosine. The synthesis occurred together with the photo-oxidation of bases in a complex process for which possible pathways are proposed. In conclusion, an acetylene-containing atmosphere could contribute to the origin of nucleobases in the presence of a urea/water system by an HCN-independent mechanism. The presence of ice has a dual role as a favorable medium for the synthesis of nucleobases and protection against degradation and as a source of free radicals for the synthesis of highly oxidized heterocycles. A mechanism for the origin of hydantoins and uracil from urea in plausible conditions for prebiotic chemistry is also proposed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visualizing Viral Protein Structures in Cells Using Genetic Probes for Correlated Light and Electron Microscopy

PubMed Central

Ou, Horng D.; Deerinck, Thomas J.; Bushong, Eric; Ellisman, Mark H.; O’Shea, Clodagh C.

2015-01-01

Structural studies of viral proteins most often use high-resolution techniques such as X-ray crystallography, nuclear magnetic resonance, single particle negative stain, or cryo-electron microscopy (EM) to reveal atomic interactions of soluble, homogeneous viral proteins or viral protein complexes. Once viral proteins or complexes are separated from their host’s cellular environment, their natural in-situ structure and details of how they interact with other cellular components may be lost. EM has been an invaluable tool in virology since its introduction in the late 1940’s and subsequent application to cells in the 1950’s. EM studies have expanded our knowledge of viral entry, viral replication, alteration of cellular components, and viral lysis. Most of these early studies were focused on conspicuous morphological cellular changes, because classic EM metal stains were designed to highlight classes of cellular structures rather than specific molecular structures. Much later, to identify viral proteins inducing specific structural configurations at the cellular level, immunostaining with a primary antibody followed by colloidal gold secondary antibody was employed to mark the location of specific viral proteins. This technique can suffer from artifacts in cellular ultrastructure due to compromises required to provide access to the immuno-reagents. Immunolocalization methods also require the generation of highly specific antibodies, which may not be available for every viral protein. Here we discuss new methods to visualize viral proteins and structures at high resolutions in-situ using correlated light and electron microscopy (CLEM). We discuss the use of genetically encoded protein fusions that oxidize diaminobenzidine (DAB) into an osmiophilic polymer that can be visualized by EM. Detailed protocols for applying the genetically encoded photo-oxidizing protein MiniSOG to a viral protein, photo-oxidation of the fusion protein to yield DAB polymer staining, and preparation of photo-oxidized samples for TEM and serial block-face scanning EM (SBEM) for large-scale volume EM data acquisition are also presented. As an example, we discuss the recent multi-scale analysis of Adenoviral protein E4-ORF3 that reveals a new type of multi-functional polymer that disrupts multiple cellular proteins. This new capability to visualize unambiguously specific viral protein structures at high resolutions in the native cellular environment is revealing new insights into how they usurp host proteins and functions to drive pathological viral replication. PMID:26066760

Visualizing viral protein structures in cells using genetic probes for correlated light and electron microscopy.

PubMed

Ou, Horng D; Deerinck, Thomas J; Bushong, Eric; Ellisman, Mark H; O'Shea, Clodagh C

2015-11-15

Structural studies of viral proteins most often use high-resolution techniques such as X-ray crystallography, nuclear magnetic resonance, single particle negative stain, or cryo-electron microscopy (EM) to reveal atomic interactions of soluble, homogeneous viral proteins or viral protein complexes. Once viral proteins or complexes are separated from their host's cellular environment, their natural in situ structure and details of how they interact with other cellular components may be lost. EM has been an invaluable tool in virology since its introduction in the late 1940's and subsequent application to cells in the 1950's. EM studies have expanded our knowledge of viral entry, viral replication, alteration of cellular components, and viral lysis. Most of these early studies were focused on conspicuous morphological cellular changes, because classic EM metal stains were designed to highlight classes of cellular structures rather than specific molecular structures. Much later, to identify viral proteins inducing specific structural configurations at the cellular level, immunostaining with a primary antibody followed by colloidal gold secondary antibody was employed to mark the location of specific viral proteins. This technique can suffer from artifacts in cellular ultrastructure due to compromises required to provide access to the immuno-reagents. Immunolocalization methods also require the generation of highly specific antibodies, which may not be available for every viral protein. Here we discuss new methods to visualize viral proteins and structures at high resolutions in situ using correlated light and electron microscopy (CLEM). We discuss the use of genetically encoded protein fusions that oxidize diaminobenzidine (DAB) into an osmiophilic polymer that can be visualized by EM. Detailed protocols for applying the genetically encoded photo-oxidizing protein MiniSOG to a viral protein, photo-oxidation of the fusion protein to yield DAB polymer staining, and preparation of photo-oxidized samples for TEM and serial block-face scanning EM (SBEM) for large-scale volume EM data acquisition are also presented. As an example, we discuss the recent multi-scale analysis of Adenoviral protein E4-ORF3 that reveals a new type of multi-functional polymer that disrupts multiple cellular proteins. This new capability to visualize unambiguously specific viral protein structures at high resolutions in the native cellular environment is revealing new insights into how they usurp host proteins and functions to drive pathological viral replication. Copyright © 2015 Elsevier Inc. All rights reserved.

Leaves of field-grown mastic trees suffer oxidative stress at the two extremes of their lifespan.

PubMed

Juvany, Marta; Müller, Maren; Munné-Bosch, Sergi

2012-08-01

Leaf senescence is a complex phenomenon occurring in all plant species, but it is still poorly understood in plants grown in Mediterranean field conditions and well-adapted to harsh climatic conditions. To better understand the physiological processes underlying leaf senescence in mastic trees (Pistacia lentiscus L.), we evaluated leaf growth, water and N content, photosystem II (PSII) photochemistry, lipid peroxidation and levels of photosynthetic pigments, antioxidants, abscisic acid, and salicylic acid and jasmonic acid during the complete leaf lifespan, from early expansion to late senescence in relation to natural climatic conditions in the field. While mature leaves suffered from water and N deficit during late spring and summer, both young (emerging) and old (senescing) leaves were most sensitive to photo-oxidative stress, as indicated by reductions in the F(v)/F(m) ratio and enhanced lipid peroxidation during late autumn and winter. Reductions in the F(v)/F(m) ratio were associated with low α-tocopherol (vitamin E) levels, while very old, senescing leaves additionally showed severe anthocyanin losses. We have concluded that both young (emerging) and old (senescing) leaves suffer oxidative stress in mastic trees, which may be linked in part to suboptimal temperatures during late autumn and winter as well as to low vitamin E levels. © 2012 Institute of Botany, Chinese Academy of Sciences.

Purification and preconcentration of genomic DNA from whole cell lysates using photoactivated polycarbonate (PPC) microfluidic chips

PubMed Central

Witek, Małgorzata A.; Llopis, Shawn D.; Wheatley, Abigail; McCarley, Robin L.; Soper, Steven A.

2006-01-01

We discuss the use of a photoactivated polycarbonate (PPC) microfluidic chip for the solid-phase, reversible immobilization (SPRI) and purification of genomic DNA (gDNA) from whole cell lysates. The surface of polycarbonate was activated by UV radiation resulting in a photo-oxidation reaction, which produced a channel surface containing carboxylate groups. The gDNA was selectively captured on this photoactivated surface in an immobilization buffer, which consisted of 3% polyethylene glycol, 0.4 M NaCl and 70% ethanol. The methodology reported herein is similar to conventional SPRI in that surface-confined carboxylate groups are used for the selective immobilization of DNA; however, no magnetic beads or a magnetic field are required. As observed by UV spectroscopy, a load of ∼7.6 ± 1.6 µg/ml of gDNA was immobilized onto the PPC bed. The recovery of DNA following purification was estimated to be 85 ± 5%. The immobilization and purification assay using this PPC microchip could be performed within ∼25 min as follows: (i) DNA immobilization ∼6 min, (ii) chip washout with ethanol 10 min, and (iii) drying and gDNA desorption ∼6 min. The PPC microchip could also be used for subsequent assays with no substantial loss in recovery, no observable carryover and no need for ‘reactivation’ of the PC surface with UV light. PMID:16757572

Nuclear Photosynthetic Gene Expression Is Synergistically Modulated by Rates of Protein Synthesis in Chloroplasts and Mitochondria[W

PubMed Central

Pesaresi, Paolo; Masiero, Simona; Eubel, Holger; Braun, Hans-Peter; Bhushan, Shashi; Glaser, Elzbieta; Salamini, Francesco; Leister, Dario

2006-01-01

Arabidopsis thaliana mutants prors1-1 and -2 were identified on the basis of a decrease in effective photosystem II quantum yield. Mutations were localized to the 5′-untranslated region of the nuclear gene PROLYL-tRNA SYNTHETASE1 (PRORS1), which acts in both plastids and mitochondria. In prors1-1 and -2, PRORS1 expression is reduced, along with protein synthesis in both organelles. PRORS1 null alleles (prors1-3 and -4) result in embryo sac and embryo development arrest. In mutants with the leaky prors1-1 and -2 alleles, transcription of nuclear genes for proteins involved in photosynthetic light reactions is downregulated, whereas genes for other chloroplast proteins are upregulated. Downregulation of nuclear photosynthetic genes is not associated with a marked increase in the level of reactive oxygen species in leaves and persists in the dark, suggesting that the transcriptional response is light and photooxidative stress independent. The mrpl11 and prpl11 mutants are impaired in the mitochondrial and plastid ribosomal L11 proteins, respectively. The prpl11 mrpl11 double mutant, but neither of the single mutants, resulted in strong downregulation of nuclear photosynthetic genes, like that seen in leaky mutants for PRORS1, implying that, when organellar translation is perturbed, signals derived from both types of organelles cooperate in the regulation of nuclear photosynthetic gene expression. PMID:16517761

The family of light-harvesting-related proteins (LHCs, ELIPs, HLIPs): was the harvesting of light their primary function?

PubMed

Montané, M H; Kloppstech, K

2000-11-27

Light-harvesting complex proteins (LHCs) and early light-induced proteins (ELIPs) are essential pigment-binding components of the thylakoid membrane and are encoded by one of the largest and most complex higher plant gene families. The functional diversification of these proteins corresponded to the transition from extrinsic (phycobilisome-based) to intrinsic (LHC-based) light-harvesting antenna systems during the evolution of chloroplasts from cyanobacteria, yet the functional basis of this diversification has been elusive. Here, we propose that the original function of LHCs and ELIPs was not to collect light and to transfer its energy content to the reaction centers but to disperse the absorbed energy of light in the form of heat or fluorescence. These energy-dispersing proteins are believed to have originated in cyanobacteria as one-helix, highly light-inducible proteins (HLIPs) that later acquired four helices through two successive gene duplication steps. We suggest that the ELIPs arose first in this succession, with a primary function in energy dispersion for protection of photosynthetic pigments from photo-oxidation. We consider the LHC I and II families as more recent and very successful evolutionary additions to this family that ultimately attained a new function, thereby replacing the ancestral extrinsic light-harvesting system. Our model accounts for the non-photochemical quenching role recently shown for higher plant psbS proteins.

Inhibition of Seagrass Photosynthesis by Ultraviolet-B Radiation 1

PubMed Central

Trocine, Robert P.; Rice, John D.; Wells, Gary N.

1981-01-01

Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme Kütz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated. Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. This mechanism effectively attenuated photosynthetic inhibition induced by ultraviolet-B dose rates and dosages in excess of natural conditions. Syringodium appeared to rely primarily on a thick epidermal cell layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species. Observations obtained in this study seem to suggest the possibility of anthocyanin and/or other flavonoid synthesis as an adaptation to long term ultraviolet-B irradiation by these species. In addition, Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation. Images PMID:16661893

Rhodobacter sp. Rb3, an aerobic anoxygenic phototroph which thrives in the polyextreme ecosystem of the Salar de Huasco, in the Chilean Altiplano.

PubMed

Pérez, Vilma; Dorador, Cristina; Molina, Verónica; Yáñez, Carolina; Hengst, Martha

2018-03-22

The Salar de Huasco is an evaporitic basin located in the Chilean Altiplano, which presents extreme environmental conditions for life, i.e. high altitude (3800 m.a.s.l.), negative water balance, a wide salinity range, high daily temperature changes and the occurrence of the highest registered solar radiation on the planet (> 1200 W m -2 ). This ecosystem is considered as a natural laboratory to understand different adaptations of microorganisms to extreme conditions. Rhodobacter, an anoxygenic aerobic phototrophic bacterial genus, represents one of the most abundant groups reported based on taxonomic diversity surveys in this ecosystem. The bacterial mat isolate Rhodobacter sp. strain Rb3 was used to study adaptation mechanisms to stress-inducing factors potentially explaining its success in a polyextreme ecosystem. We found that the Rhodobacter sp. Rb3 genome was characterized by a high abundance of genes involved in stress tolerance and adaptation strategies, among which DNA repair and oxidative stress were the most conspicuous. Moreover, many other molecular mechanisms associated with oxidative stress, photooxidation and antioxidants; DNA repair and protection; motility, chemotaxis and biofilm synthesis; osmotic stress, metal, metalloid and toxic anions resistance; antimicrobial resistance and multidrug pumps; sporulation; cold shock and heat shock stress; mobile genetic elements and toxin-antitoxin system were detected and identified as potential survival mechanism features in Rhodobacter sp. Rb3. In total, these results reveal a wide set of strategies used by the isolate to adapt and thrive under environmental stress conditions as a model of polyextreme environmental resistome.

Integrated photooxidative-extractive desulfurization system for fuel oil using Cu, Fe and Cu-Fe/TiO2 and eutectic based ionic liquids: Effect of calcination temperature and duration

NASA Astrophysics Data System (ADS)

Zaid, Hayyiratul Fatimah Mohd; Kait, Chong Fai; Mutalib, Mohamed Ibrahim Abdul

2014-10-01

Photocatalyts TiO2 doped with Cu, Fe and Cu-Fe metal at different calcination temperature and duration were successfully prepared and characterized. Photocatalytic oxidative desulfurization of model oil containing dibenzothiophene as the sulfur compound (100 ppm) using the prepared photocatalyst was investigated. The photocatalyst calcined at 500°C and duration of 1 h showed the best performance.

Biologically Inspired Materials for Electro-Responsive Coatings and the Photo-Oxidation of Water

DTIC Science & Technology

2010-02-01

believed to be the first non-sacrificial electron acceptor capable of driving the metalloporphyrin- sensitized photocatalytic oxidation of water. Thesis ...passionate about, Angie encouraged and empowered me to keep trying new ideas. With her help, I was able to develop my thesis studies of photocatalytic...year and was a part of nearly every piece of this thesis . Throughout the thesis I try to acknowledge data that was acquired or analyzed by someone

Photooxidation of mixed aryl and biarylphosphines.

PubMed

Zhang, Dong; Celaje, Jeff A; Agua, Alon; Doan, Chad; Stewart, Timothy; Bau, Robert; Selke, Matthias

2010-07-02

Arylphosphines and dialkylbiarylphosphines react with singlet oxygen to form phosphine oxides and phosphinate esters. For mixed arylphosphines, the most electron-rich aryl group migrates to form the phosphinate, while for dialkylbiarylphosphines migration of the alkyl group occurs. Dialkylbiarylphosphines also yield arene epoxides, especially in electron-rich systems. Phosphinate ester formation is increased at high temperature, while protic solvents increase the yield of epoxide. The product distribution provides evidence for Buchwald's recent conformational model for the aerobic oxidation of dialkylbiarylphosphines.

Controlling Synergistic Oxidation Processes for Efficient and Stable Blue Thermally Activated Delayed Fluorescence Devices.

PubMed

Cui, Lin-Song; Deng, Ya-Li; Tsang, Daniel Ping-Kuen; Jiang, Zuo-Quan; Zhang, Qisheng; Liao, Liang-Sheng; Adachi, Chihaya

2016-09-01

Efficient sky-blue organic light-emitting diodes (OLEDs) employing thermally activated delayed fluorescence (TADF) display a three orders of magnitude increase in lifetime, which is superior to those of controlled phosphorescent OLEDs used in this study. The combination of electro-oxidation and photo-oxidation of the TADF emitters in their triplet excited-states is suppressed through molecule design and device engineering. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional and Cellular Responses to Laser Injury in the Rat Snake Retina

DTIC Science & Technology

2007-01-01

snake retina, previous studies have documented the role of photo-oxidative stress in inducing photoreceptor damage . 20 The present research was designed...Tyrrell, "Activation of NF-kappa B in human skin fibroblasts by the oxidative stress generated by UVA radiation," Photochem. Photobiol., 62, pp. 463-468...induced retinal photoreceptor damage .9. 10 In addition to its imaging capabilities, the cSLO can also be modulated externally to produce stimulus patterns

Computational Investigations on Enzymatic Catalysis and Inhibition

NASA Astrophysics Data System (ADS)

Simard, Daniel

Enzymes are the bimolecular "workhorses" of the cell due to their range of functions and their requirement for cellular success. The atomistic details of how they function can provide key insights into the fundamentals of catalysis and in turn, provide a blueprint for biotechnological advances. A wide range of contemporary computational techniques has been applied with the aim to characterize recently discovered intermediates or to provide insights into enzymatic mechanisms and inhibition. More specifically, an assessment of methods was conducted to evaluate the presence of the growing number 3-- and 4--coordinated sulfur intermediates in proteins/enzymes. Furthermore, two mechanisms have been investigated, the mu-OH mechanism of the hydrolysis of dimethylphosphate in Glycerophosphodiesterase (GpdQ) using five different homonuclear metal combinations Zn(II)/Zn(II), Co(II)/Co(II), Mn(II)/Mn(II), Cd(II)/Cd(II) and Ca(II)/Ca(II) as well as a preliminary study into the effectivness of boron as an inhibitor in the serine protease reaction of class A TEM-1 beta-lactamases.

RpoH2 sigma factor controls the photooxidative stress response in a non-photosynthetic rhizobacterium, Azospirillum brasilense Sp7.

PubMed

Kumar, Santosh; Rai, Ashutosh Kumar; Mishra, Mukti Nath; Shukla, Mansi; Singh, Pradhyumna Kumar; Tripathi, Anil Kumar

2012-12-01

Bacteria belonging to the Alphaproteobacteria normally harbour multiple copies of the heat shock sigma factor (known as σ(32), σ(H) or RpoH). Azospirillum brasilense, a non-photosynthetic rhizobacterium, harbours five copies of rpoH genes, one of which is an rpoH2 homologue. The genes around the rpoH2 locus in A. brasilense show synteny with that found in rhizobia. The rpoH2 of A. brasilense was able to complement the temperature-sensitive phenotype of the Escherichia coli rpoH mutant. Inactivation of rpoH2 in A. brasilense results in increased sensitivity to methylene blue and to triphenyl tetrazolium chloride (TTC). Exposure of A. brasilense to TTC and the singlet oxygen-generating agent methylene blue induced several-fold higher expression of rpoH2. Comparison of the proteome of A. brasilense with its rpoH2 deletion mutant and with an A. brasilense strain overexpressing rpoH2 revealed chaperone GroEL, elongation factors (Ef-Tu and EF-G), peptidyl prolyl isomerase, and peptide methionine sulfoxide reductase as the major proteins whose expression was controlled by RpoH2. Here, we show that the RpoH2 sigma factor-controlled photooxidative stress response in A. brasilense is similar to that in the photosynthetic bacterium Rhodobacter sphaeroides, but that RpoH2 is not involved in the detoxification of methylglyoxal in A. brasilense.

Or mutation leads to photo-oxidative stress responses in cauliflower (Brassica oleracea) seedlings during de-etiolation.

PubMed

Men, Xiao; Dong, Kang

2013-11-01

The Orange (Or) gene is a gene mutation that can increase carotenoid content in plant tissues normally devoid of pigments. It affects plastid division and is involved in the differentiation of proplastids or non-colored plastids into chromoplasts. In this study, the de-etiolation process of the wild type (WT) cauliflower (Brassica oleracea L. var. botrytis) and Or mutant seedlings was investigated. We analyzed pigment content, plastid development, transcript abundance and protein levels of genes involved in the de-etiolation process. The results showed that Or can increase the carotenoid content in green tissues, although not as effectively as in non-green tissues, and this effect might be caused by the changes in biosynthetic pathway genes at both transcriptional and post-transcriptional levels. There was no significant difference in the plastid development process between the two lines. However, the increased content of antheraxanthin and anthocyanin, and higher expression levels of violaxanthin de-epoxidase gene (VDE) suggested a stress situation leading to photoinhibition and enhanced photoprotection in the Or mutant. The up-regulated expression levels of the reactive oxygen species (ROS)-induced genes, ZAT10 for salt tolerance zinc finger protein and ASCORBATE PEROXIDASE2 (APX2), suggested the existence of photo-oxidative stress in the Or mutant. In summary, abovementioned findings provide additional insight into the functions of the Or gene in different tissues and at different developmental stages.

Asphaltene content and composition as a measure of Deepwater Horizon oil spill losses within the first 80 days

USGS Publications Warehouse

Lewan, M.D.; Warden, A.; Dias, R.F.; Lowry, Z.K.; Hannah, T.L.; Lillis, P.G.; Kokaly, R.F.; Hoefen, T.M.; Swayze, G.A.; Mills, C.T.; Harris, S.H.; Plumlee, G.S.

2014-01-01

The composition and content of asphaltenes in spilled and original wellhead oils from the Deepwater Horizon (DWH) incident provide information on the amount of original oil lost and the processes most responsible for the losses within the first 80 days of the active spill. Spilled oils were collected from open waters, coastal waters and coastal sediments during the incident. Asphaltenes are the most refractory component of crude oils but their alteration in the spilled oils during weathering prevents them from being used directly as a conservative component to calculate original oil losses. The alteration is reflected by their increase in oxygen content and depletion in 12C. Reconnaissance experiments involving evaporation, photo-oxidation, microbial degradation, dissolution, dispersion and burning indicate that the combined effects of photo-oxidation and evaporation are responsible for these compositional changes. Based on measured losses and altered asphaltenes from these experiments, a mean of 61 ± 3 vol% of the original oil was lost from the surface spilled oils during the incident. This mean percentage of original oil loss is considerably larger than previous estimates of evaporative losses based on only gas chromatography (GC) amenable hydrocarbons (32–50 vol%), and highlights the importance of using asphaltenes, as well as GC amenable parameters in evaluating original oil losses and the processes responsible for the losses.

Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.

PubMed

Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G

2016-08-01

Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation. Copyright © 2016 Elsevier B.V. All rights reserved.

Sandwich-like TiO2@ZnO-based noble metal (Ag, Au, Pt, or Pd) for better photo-oxidation performance: Synergistic effect between noble metal and metal oxide phases

NASA Astrophysics Data System (ADS)

Li, Shunxing; Cai, Jiabai; Wu, Xueqing; Zheng, Fengying

2018-06-01

The performance of different noble metals (NMs) with controllable size (5 nm) as co-catalyst on the photocatalytic oxidation of TiO2@ZnO hollow spheres was tested with benzyl alcohol in the presence of water under ambient conditions. A new type of solar-light-driven TiO2@NMs@ZnO nanocomposite was fabricated by using a template (surface functionalized polystyrene balls), hydrothermal reaction, and calcination. Under simulated sunlight irradiation, the photo-oxidation rate of benzyl alcohol was in the following of TiO2@Ag@ZnO > TiO2@Au@ZnO > TiO2@Pt@ZnO > TiO2@Pd@ZnO > TiO2@ZnO. This result was due to the combination of TiO2 and ZnO, as well as the sandwiched Ag NPs as electron trap site, which can store and shuttle photo-generated electrons, and then enhance photo-generation of active radicals. Electron paramagnetic resonance (EPR) spectroscopy, as well as photo-luminescence (PL), photo-reduction of Cr(VI) and electrochemical measurements were taken to verify this conclusion. Taking into account the multi-functional combination of precious metals and semiconductor materials, this work could provide new insights for the design of high-performance photocatalysts.

A novel astaxanthin-binding photooxidative stress-inducible aqueous carotenoprotein from a eukaryotic microalga isolated from asphalt in midsummer.

PubMed

Kawasaki, Shinji; Mizuguchi, Keisuke; Sato, Masaru; Kono, Tetsuya; Shimizu, Hirofumi

2013-07-01

Water-soluble orange carotenoid proteins (OCPs) that bind 3'-hydroxyechinenone are found in cyanobacteria, and are thought to play a key role in photoprotection. The distribution of OCPs in eukaryotes remains largely unknown. In this study, we identified a novel OCP that predominantly binds astaxanthin from a eukaryotic microalga, strain Ki-4, isolated from a dry surface of heated asphalt in midsummer. A purified astaxanthin-binding OCP, named AstaP, shows high solubility in water with an absorption peak at 484 nm, and possesses a heat-stable activity that quenches singlet oxygen. The deduced amino acid sequence of AstaP comprises an N-terminal hydrophobic signal peptide, fasciclin domains found in secreted and cell surface proteins, and N-linked glycosylation sites, the first example of a carotenoprotein among fasciclin family proteins. AstaP homologs of unknown function are distributed mainly in organisms from the hydrosphere, such as marine bacteria, cyanobacteria, sea anemone and eukaryotic microalgae; however, AstaP exhibits a unique extraordinarily high isoelectric point (pI) value among homologs. The gene encoding AstaP, as well as the AstaP peptide, is expressed abundantly under conditions of dehydration and salt stress in conjunction with high light exposure. As a unique aqueous carotenoprotein, AstaP will provide a novel function of OCPs in protection against extreme photooxidative stresses.

Secondary Organic Aerosol and Brown Carbon Formation in the Sunlit Aqueous Phase: Aldehyde Photooxidation in the Presence of Ammonium Salts and Amines

NASA Astrophysics Data System (ADS)

De Haan, D. O.; Galloway, M. M.; Sharp, K. D.; Jiménez, N. G.

2014-12-01

The chemistry of water-soluble carbonyl compounds in clouds is now acknowledged as an important source of secondary organic aerosol. These reactive carbonyl compounds are oxidized to carboxylic acids and form oligomers by radical-radical reactions and by "dark reactions" with ammonium salts (AS) and/or amines. The latter class of reactions also produces light-absorbing brown carbon compounds, especially reactions involving methylglyoxal or glyoxal and amines. However, recent work has found that UV light fades the color of glyoxal + AS and methylgyloxal + AS reaction mixtures. We recently studied aldehyde-AS-amine reactions in sunlight and in control vessels at the same temperature to determine the effects of solar radiation on the aqueous-phase production of brown carbon. In sunlight, methylglyoxal reaction mixtures lost their initial color and failed to brown, indicating the photolytic loss of reactants and/or pre-brown intermediates. In many other reactions, brown products are lost to photolysis, reducing the overall browning of solutions exposed to sunlight. In other experiments, hydrogen peroxide was added to generate OH radicals by photolysis. In the presence of OH radicals, some carbonyl compound mixtures (e.g. those containing hydroxyacetone or glycolaldehyde) browned more rapidly when exposed to sunlight. This indicates the existence of uncharacterized photooxidative browning pathways involving aqueous-phase OH radicals, carbonyls, ammonium salts, and/or amine compounds.

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

PubMed Central

Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

2013-01-01

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

PubMed

Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

2013-07-16

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

Recent developments in photocatalytic water treatment technology: a review.

PubMed

Chong, Meng Nan; Jin, Bo; Chow, Christopher W K; Saint, Chris

2010-05-01

In recent years, semiconductor photocatalytic process has shown a great potential as a low-cost, environmental friendly and sustainable treatment technology to align with the "zero" waste scheme in the water/wastewater industry. The ability of this advanced oxidation technology has been widely demonstrated to remove persistent organic compounds and microorganisms in water. At present, the main technical barriers that impede its commercialisation remained on the post-recovery of the catalyst particles after water treatment. This paper reviews the recent R&D progresses of engineered-photocatalysts, photoreactor systems, and the process optimizations and modellings of the photooxidation processes for water treatment. A number of potential and commercial photocatalytic reactor configurations are discussed, in particular the photocatalytic membrane reactors. The effects of key photoreactor operation parameters and water quality on the photo-process performances in terms of the mineralization and disinfection are assessed. For the first time, we describe how to utilize a multi-variables optimization approach to determine the optimum operation parameters so as to enhance process performance and photooxidation efficiency. Both photomineralization and photo-disinfection kinetics and their modellings associated with the photocatalytic water treatment process are detailed. A brief discussion on the life cycle assessment for retrofitting the photocatalytic technology as an alternative waste treatment process is presented. This paper will deliver a scientific and technical overview and useful information to scientists and engineers who work in this field.

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

DOE PAGES

Liu, Yingjun; Seco, Roger; Kim, Saewung; ...

2018-04-11

Nitrogen oxides (NO x) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning.more » The afternoon concentrations of reactive nitrogen oxides (NO y), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3. The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.« less

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yingjun; Seco, Roger; Kim, Saewung

Nitrogen oxides (NO x) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning.more » The afternoon concentrations of reactive nitrogen oxides (NO y), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3. The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.« less

Development of Active Films From Pectin and Fruit Extracts: Light Protection, Antioxidant Capacity, and Compounds Stability.

PubMed

Eça, Kaliana S; Machado, Mariana T C; Hubinger, Miriam D; Menegalli, Florencia C

2015-11-01

Pectin films containing fruit extracts were developed and tested in relation to ultraviolet light transmission, phytochemical contents, and antioxidant capacity during 90 d shelf life storage. Aqueous and alcoholic extracts from 5 different fruits (acerola, cashew apple, papaya, pequi, and strawberry) were obtained. Because the alcoholic extracts from acerola, cashew apple, and strawberry presented the highest phytochemical content and antioxidant capacity, they were incorporated into pectin films individually or as a mixture. Incorporation of these extracts into pectin films provided antioxidant capacity while retaining the physical properties. The pectin films containing fruit extract acted as adequate light barrier and prevented photooxidation. Among the prepared films, the pectin film containing acerola extract afforded the highest antioxidant capacity, with a half-life of 99 d. Overall, the results revealed that incorporation of fruit extracts into pectin films potentially produces antioxidant films and coatings for different food applications. The production of pectin films incorporated with fruit extract is based on combination of the antioxidant activity, natural color, and optical barrier properties from fruit phytochemical components to the active film. This film could be potentially used as active packing on food products in order to protect their nutrients against free radicals action and photooxidation and, hence, preserve the quality, integrity, and safety of food during the storage period. © 2015 Institute of Food Technologists®

The atmospheric degradation of methyl isocyanate (CH3NCO), a toxic substance

NASA Astrophysics Data System (ADS)

Papanastasiou, D. K.; Bernard, F.; Burkholder, J. B.

2016-12-01

Alkyl isocyanates (R-NCO), as well as isocyanic acid (HNCO), are toxic substances that are emitted into the atmosphere during incomplete combustion of biomass and also formed as products in the atmospheric photooxidation of nitrogen-containing organic species. For example, methyl isocyanate (MIC, CH3NCO) is formed in the atmospheric photochemical transformation of methylisothiocyanate (CH3NCS), a widely used soil fumigant, as well as in the atmospheric photooxidation of amides, such as N-methylformamide. MIC is of particular interest to society because of the possible exposure to this toxic trace compound (recommended exposure limit is 0.02 ppm) in the aftermath of fumigation. Although, there are limited observations of atmospheric MIC (mostly nearby agricultural/fumigation activities) the possibility of emission from combustion processes, such as wildfires, warrants future study. The atmospheric lifetime and fate (gas phase and heterogeneous chemistry) of CH3NCO are presently not well characterized with only a single study of the OH + CH3NCO reaction rate coefficient available in the literature. Additional results from fundamental laboratory studies regarding the major atmospheric degradation pathways of MIC are needed for input to air quality, health, and environmental impact studies. In this study, the reaction of CH3NCO with OH radicals was investigated using pulsed laser photolysis coupled with laser induced fluorescence detection of the OH radical. The rate coefficients, k(OH+CH3NCO), were determined over a range of temperature (295-375 K) and pressure (40-100 Torr, He). The present results are in significant disagreement with the recently published relative rate study. A relative rate kinetic method was also used in this study for comparison and the problems associated with these measurements will be discussed. The atmospheric lifetime of MIC with respect to its gas-phase reaction with OH radicals is estimated to be 85 days, which implies the possibility for long-range transport. In addition, the UV absorption spectrum of CH3NCO at 295 K was measured between 185 and 260 nm and UV photolysis is considered to be a relatively minor atmospheric loss process. The importance of gas phase and heterogeneous removal processes for CH3NCO and the atmospheric degradation mechanism will be discussed.

Enhancing the efficacy of AREDS antioxidants in light-induced retinal degeneration

PubMed Central

Wong, Paul; Markey, M.; Rapp, C. M.; Darrow, R. M.; Ziesel, A.

2017-01-01

Purpose Light-induced photoreceptor cell degeneration and disease progression in age-related macular degeneration (AMD) involve oxidative stress and visual cell loss, which can be prevented, or slowed, by antioxidants. Our goal was to test the protective efficacy of a traditional Age-related Eye Disease Study antioxidant formulation (AREDS) and AREDS combined with non-traditional antioxidants in a preclinical animal model of photooxidative retinal damage. Methods Male Sprague-Dawley rats were reared in a low-intensity (20 lux) or high-intensity (200 lux) cyclic light environment for 6 weeks. Some animals received a daily dietary supplement consisting of a small cracker infused with an AREDS antioxidant mineral mixture, AREDS antioxidants minus zinc, or zinc oxide alone. Other rats received AREDS combined with a detergent extract of the common herb rosemary, AREDS plus carnosic acid, zinc oxide plus rosemary, or rosemary alone. Antioxidant efficacy was determined by measuring retinal DNA levels 2 weeks after 6 h of intense exposure to white light (9,000 lux). Western blotting was used to determine visual cell opsin and arrestin levels following intense light treatment. Rhodopsin regeneration was determined after 1 h of exposure to light. Gene array analysis was used to determine changes in the expression of retinal genes resulting from light rearing environment or from antioxidant supplementation. Results Chronic high-intensity cyclic light rearing resulted in lower levels of rod and cone opsins, retinal S-antigen (S-ag), and medium wavelength cone arrestin (mCAR) than found for rats maintained in low cyclic light. However, as determined by retinal DNA, and by residual opsin and arrestin levels, 2 weeks after acute photooxidative damage, visual cell loss was greater in rats reared in low cyclic light. Retinal damage decreased with AREDS plus rosemary, or with zinc oxide plus rosemary whereas AREDS alone and zinc oxide alone (at their daily recommended levels) were both ineffective. One week of supplemental AREDS plus carnosic acid resulted in higher levels of rod and cone cell proteins, and higher levels of retinal DNA than for AREDS alone. Rhodopsin regeneration was unaffected by the rosemary treatment. Retinal gene array analysis showed reduced expression of medium- wavelength opsin 1 and arrestin C in the high-light reared rats versus the low-light rats. The transition of rats from low cyclic light to a high cyclic light environment resulted in the differential expression of 280 gene markers, enriched for genes related to inflammation, apoptosis, cytokine, innate immune response, and receptors. Rosemary, zinc oxide plus rosemary, and AREDS plus rosemary suppressed 131, 241, and 266 of these genes (respectively) in high-light versus low-light animals and induced a small subset of changes in gene expression that were independent of light rearing conditions. Conclusions Long-term environmental light intensity is a major determinant of retinal gene and protein expression, and of visual cell survival following acute photooxidative insult. Rats preconditioned by high-light rearing exhibit lower levels of cone opsin mRNA and protein, and lower mCAR protein, than low-light reared animals, but greater retention of retinal DNA and proteins following photooxidative damage. Rosemary enhanced the protective efficacy of AREDS and led to the greatest effect on the retinal genome in animals reared in high environmental light. Chronic administration of rosemary antioxidants may be a useful adjunct to the therapeutic benefit of AREDS in slowing disease progression in AMD. PMID:29062223

Chemistry of the 1,2-Dioxetane Ring System. Chemiluminescence, Fragmentations, and Catalyzed Rearrangements.

DTIC Science & Technology

1978-04-18

experimental techniques and for an historical perspective on the chemistry of l,2—dioxetanes. Synthesis and Structure of l,2—Dioxetanes There are at...is relatively electron rich and does not contain abstractable allylic hydrogen atoms . The advantage of the photooxidation , of course , is the...however , is that the phenol is acting as an acid causing the rapid dark path reaction of the dioxetane and hence giving rise to an ap- parent large

Theoretical Bases of Polymer Photodegradation and Photooxidation,

DTIC Science & Technology

1987-10-15

UNCLASSIFIED FTD- AD(RS)T-E868-87 F/G 7/6 NL MhEEOEE~~h EhiIIIEEEEEI -M Mi(ROC PY RESOLUtIO(N TEST CHA NA ION- A j ~A M R ~ . DEiC FILE CME ( 1 ) FTD-ID...In addition, when such processes are carried out in an atmosphere of air, numerous carbonyl, carboxyl , hydroxyl etc. groups form along the polymer...photoaging this should be multilateral with consideration of the following basic processes [ 1 -93: ...... 1 . Photochemical reactions of the actual

Study of holograms made with saccharides and iron ions

NASA Astrophysics Data System (ADS)

Ordóñez-Padilla, M. M.; Olivares-Pérez, A.; Dorantes-García, V.; Vallejo-Mendoza, R.; Fuentes-Tapia, I.

2012-03-01

We present the performance characterization of photosensitive film emulsions prepared with saccharides like: pectin, fructose and sugar (Glass ®), at certain physicochemical conditions for holographic recording. The photo-oxidation was carried out with concentrations of iron ions, Fe+3. We analyzed the parameters of the diffraction efficiencies of each grating constructed with saccharides film. The work was to achieve stability and non-toxicity of the films prepared easily with water-Fe ions. We performed an experimental comparison of the holographic films capacity between the three saccharides.

Photooxidation of Mixed Aryl and Biarylphosphines

PubMed Central

Zhang, Dong; Celaje, Jeff A.; Agua, Alon; Doan, Chad; Stewart, Timothy; Bau, Robert; Selke, Matthias

2010-01-01

Aryl phosphines and dialkylbiaryl phosphines react with singlet oxygen to form phosphinate esters. For mixed arylphosphines, the most electron-rich aryl group migrates to form the phosphinate, while for dialkylbiaryl phosphines migration of the alkyl group occurs. Dialkylbiaryl phosphines also yield arene epoxides, especially in electron rich systems. Phosphinate ester formation is increased at high temperature while protic solvents increase the yield of epoxide. The product distribution provides evidence for Buchwald’s recent conformational model for the aerobic oxidation of dialkylbiaryl phosphines. PMID:20527907

Photochemistry and photooxidation of tetraphenyl-p-dioxin

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, M.V.; Kumar, C.V.; Scaiano, J.C.

1979-09-20

Laser flash photolysis studies of tetraphenyl-p-dioxin have led to the characterization of its triplet state. The T-T absorption spectra shows maxima at 350 and 545 nm; the triplet has a lifetime of 535 ns in methanol and can be quenched by di-tert-butyl nitroxide, paraquat dications, oxygen, and di-tert-butyl selenoketone. The interaction of the triplet with oxygen leads to the formation of singlet oxygen which in turn reacts with the title compound to yield benzil.

Online monitoring of a photocatalytic reaction by real-time high resolution FlowNMR spectroscopy.

PubMed

Hall, Andrew M R; Broomfield-Tagg, Rachael; Camilleri, Matthew; Carbery, David R; Codina, Anna; Whittaker, David T E; Coombes, Steven; Lowe, John P; Hintermair, Ulrich

2017-12-19

We demonstrate how FlowNMR spectroscopy can readily be applied to investigate photochemical reactions that require sustained input of light and air to yield mechanistic insight under realistic conditions. The Eosin Y mediated photo-oxidation of N-allylbenzylamine is shown to produce imines as primary reaction products from which undesired aldehydes form after longer reaction times. Facile variation of reaction conditions during the reaction in flow allows for probe experiments that give information about the mode of action of the photocatalyst.

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

PubMed

Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

2016-12-19

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center is more efficient than intermolecular electron transfer between the separate components.

An Intrinsically Disordered Photosystem II Subunit, PsbO, Provides a Structural Template and a Sensor of the Hydrogen-bonding Network in Photosynthetic Water Oxidation*

PubMed Central

Offenbacher, Adam R.; Polander, Brandon C.; Barry, Bridgette A.

2013-01-01

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global 13C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster. PMID:23940038

Computer modeling of electron and proton transport in chloroplasts.

PubMed

Tikhonov, Alexander N; Vershubskii, Alexey V

2014-07-01

Photosynthesis is one of the most important biological processes in biosphere, which provides production of organic substances from atmospheric CO2 and water at expense of solar energy. In this review, we contemplate computer models of oxygenic photosynthesis in the context of feedback regulation of photosynthetic electron transport in chloroplasts, the energy-transducing organelles of the plant cell. We start with a brief overview of electron and proton transport processes in chloroplasts coupled to ATP synthesis and consider basic regulatory mechanisms of oxygenic photosynthesis. General approaches to computer simulation of photosynthetic processes are considered, including the random walk models of plastoquinone diffusion in thylakoid membranes and deterministic approach to modeling electron transport in chloroplasts based on the mass action law. Then we focus on a kinetic model of oxygenic photosynthesis that includes key stages of the linear electron transport, alternative pathways of electron transfer around photosystem I (PSI), transmembrane proton transport and ATP synthesis in chloroplasts. This model includes different regulatory processes: pH-dependent control of the intersystem electron transport, down-regulation of photosystem II (PSII) activity (non-photochemical quenching), the light-induced activation of the Bassham-Benson-Calvin (BBC) cycle. The model correctly describes pH-dependent feedback control of electron transport in chloroplasts and adequately reproduces a variety of experimental data on induction events observed under different experimental conditions in intact chloroplasts (variations of CO2 and O2 concentrations in atmosphere), including a complex kinetics of P700 (primary electron donor in PSI) photooxidation, CO2 consumption in the BBC cycle, and photorespiration. Finally, we describe diffusion-controlled photosynthetic processes in chloroplasts within the framework of the model that takes into account complex architecture of chloroplasts and lateral heterogeneity of lamellar system of thylakoids. The lateral profiles of pH in the thylakoid lumen and in the narrow gap between grana thylakoids have been calculated under different metabolic conditions. Analyzing topological aspects of diffusion-controlled stages of electron and proton transport in chloroplasts, we conclude that along with the NPQ mechanism of attenuation of PSII activity and deceleration of PQH2 oxidation by the cytochrome b6f complex caused by the lumen acidification, the intersystem electron transport may be down-regulated due to the light-induced alkalization of the narrow partition between adjacent thylakoids of grana. The computer models of electron and proton transport described in this article may be integrated as appropriate modules into a comprehensive model of oxygenic photosynthesis. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Mechanisms of Hg(II) uptake and methylation in methylating bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morel, Francois M. M.

2016-10-14

The goal of this project was to understand the critical factors which control the availability and transport of Hg(II) into cells, a first step in the production of the neurotoxin, methylmercury. Specifically, this research focused on understanding the mechanism of bacterial mercury uptake and how mercury speciation affects the specificity and kinetics of mercury transport. Our research has shown that Hg(II) uptake in three different iron and sulfate-reducing proteobacteria occurs by the following mechanism (1) : Hg(II) uptake is an active transport process requiring energy, (2) it is dependent upon the structure of the Hg binding ligand, and (3) itmore » is mediated by a heavy metal transporter such as one which transports the essential metal, Zn(II). In order to determine whether this mechanism extends to more diverse phylogenetic groups, we have begun examining Hg(II) uptake and bioavailability in two representative Hg methylating strains within the Firmicutes. These organisms have remarkably different membrane structures distinct from the Proteobacteria. Our results show low uptake rates in these two species of Firmicutes relative to the previously characterized Proteobacteria. This may explain the low methylation rates and yields observed in these organisms. Most surprisingly, however, these organisms appear to take up Hg(II) passively, as the addition of a protonophore failed to reduce Hg(II) uptake in these organisms. This is quite different to what has been observed previously for the Proteobacteria and suggests a different mechanism for Hg(II) uptake in the Firmicutes. We are continuing to understand and describe Hg(II) uptake in these organisms. A manuscript is expected to be submitted on this research in June 2016.« less

Impact of the ion transportome of chloroplasts on the optimization of photosynthesis.

PubMed

Szabò, Ildikò; Spetea, Cornelia

2017-06-01

Ions play fundamental roles in all living cells, and their gradients are often essential to fuel transport, regulate enzyme activities, and transduce energy within cells. Regulation of their homeostasis is essential for cell metabolism. Recent results indicate that modulation of ion fluxes might also represent a useful strategy to regulate one of the most important physiological processes taking place in chloroplasts, photosynthesis. Photosynthesis is highly regulated, due to its unique role as a cellular engine for growth in the light. Controlling the balance between ATP and NADPH synthesis is a critical task, and availability of these molecules can limit the overall photosynthetic yield. Photosynthetic organisms optimize photosynthesis in low light, where excitation energy limits CO2 fixation, and minimize photo-oxidative damage in high light by dissipating excess photons. Despite extensive studies of these phenomena, the mechanism governing light utilization in plants is still poorly understood. In this review, we provide an update of the recently identified chloroplast-located ion channels and transporters whose function impacts photosynthetic efficiency in plants. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Targeting ideal acceptor-donor materials based on hexabenzocoronene

NASA Astrophysics Data System (ADS)

Santos Silva, H.; Metz, Sebastian; Hiorns, Roger C.; Bégué, D.

2018-06-01

A series of new hybrid donor-acceptor materials based on hexabenzocoronenes (HBC) functionalized with electron donors is investigated by combining a variety of quantum mechanical and molecular dynamic methodologies for use in organic photovoltaic (OPV) devices. Segments of a low band gap alternating copolymer constructed of benzo[1,2-b;3,4-b]dithiophene and thieno[3,4-c]pyrrole-4,6-dione were attached to the conjugated HBC core. The copolymer was chosen for its known high performance in OPVs, and both moieties were singled out due to their exceptional resistance to photo-oxidation, an important requirement for such applications. The macromolecular topology of these systems are expected to induce supra-molecular columns, such as those common to discotic liquid crystals, conducive to the effective percolation of electrons in OPV devices. A challenge with these systems, that of the mixing of the electronic structures of the donor and acceptor moieties that result in excitonic losses and charge recombination, was diminished by trialling a range of linking units. It was found possible to propose ideal donor-acceptor structures with enhanced charge dissociations and transfers in the π-stacking direction for use in OPV and other organic electronic devices.

Chiral templating of self-assembling nanostructures by circularly polarized light

DOE PAGES

Yeom, Jihyeon; Yeom, Bongjun; Chan, Henry; ...

2014-11-17

Chemical reactions affected by spin angular momenta of circularly polarized photons are rare and display low enantiomeric excess. High optical and chemical activity of nanoparticles (NPs) should facilitate the transfer of spin angular momenta of photons to nanoscale materials but such processes are unknown. Here we demonstrate that circularly polarized light (CPL) strongly affects self-assembly of racemic CdTe NPs. Illumination of NP dispersions with right- and left-handed CPL induces the formation of right- and left-handed twisted nanoribbons, respectively. Enantiomeric excess of such reactions exceeds 30% which is ~10 times higher than other CPL-induced reactions. Illumination with linearly polarized light andmore » assembly in the dark led to straight nanoribbons. The mechanism of “templation” of NP assemblies by CPL is associated with selective photoactivation of chiral NPs and clusters followed by their photooxidation. Chiral anisotropy of interactions translates into chirality of the assembled ribbons. Lastly, the ability of NPs to retain polarization information, or the “imprint” of incident photons opens new pathways for the synthesis of chiral photonic materials and allows for better understanding of the origins of biomolecular homochirality.« less

Ethylene formation by polymorphonuclear leukocytes. Role of myeloperoxidase

PubMed Central

1978-01-01

Ethylene formation from the thioethers, beta-methylthiopropionaldehyde (methional) and 2-keto-4-thiomethylbutyric acid by phagocytosing polymorphonuclear leukocytes (PMNs) was found to be largely dependent on myeloperoxidase (MPO). Conversion was less than 10% of normal when MPO-deficient PMNs were employed; formation by normal PMNs was inhibited by the peroxidase inhibitors, azide, and cyanide, and a model system consisting of MPO, H2O2, chloride (or bromide) and EDTA was found which shared many of the properties of the predominant PMN system. MPO-independent mechanisms of ethylene formation were also identified. Ethylene formation from methional by phagocytosing eosinophils and by H2O2 in the presence or absence of catalase was stimulated by azide. The presence of MPO-independent, azide-stimulable systems in the PMN preparations was suggested by the azide stimulation of ethylene formation from methional when MPO-deficient leukocytes were employed. Ethylene formation by dye-sensitized photooxidation was also demonstrated and evidence obtained for the involvement of singlet oxygen (1O2). These findings are discussed in relation to the participation of H2O2, hydroxyl radicals, the superoxide anion and 1O2 in the formation of ethylene by PMNs and by the MPO model system. PMID:212502

Copper resinate: preparation, characterisation and study of degradation.

PubMed

Colombini, M P; Lanterna, G; Mairani, A; Matteini, M; Modugno, F; Rizzi, M

2001-01-01

This paper describes a method for the synthesis of Copper Resinate, which disappeared from artists' palettes in the eighteenth century. This was carried out by interpreting ancient recipes following a scientific approach. Its characterisation using Fourier Transform-Infrared Spectrometry and Gas Chromatography-Mass Spectrometry demonstrated that it is a mixture containing copper and oxidised abietic acids, mainly dehydroabietic and 7-oxo-dehydroabietic acids, formed during the preparation of the pigment and the curing of the paint layer. The composition of copper resinate paint layers, artificially aged by U.V. irradiation at 365 nm (UV), heating (T), and exposed to atmospheric pollutants (NOX) in a climatic chamber, was investigated. The combination of irradiation and temperature produced a change in colour along with a significant increase in the recovered amount of 7-oxo-dehydroabietic acid. The identification of copper resinate in a sample from an old painting should be related to the presence of the following resin compounds which are stable in the ageing process: dehydroabietic and 7-oxo-dehydroabietic acid pimaradienic acids. Photo-oxidation of the resin acids co-ordinated with copper seem to be the most probable decay mechanism responsible for the colour change in the pigment.

Kinetic and mechanistic aspects of sensitized photodegradation of β-lactam antibiotics: microbiological implications.

PubMed

Reynoso, E; Nesci, A; Allegretti, P; Criado, S; Biasutti, M A

2012-01-01

Amoxicillin (Amx) and cephalexin (Cfx) are β-lactam antibiotics widely used in human and veterinary medicine. Two points of interest surrounding these molecules are the photodegradation of the molecules and their microbiological implications, as well as the persistence and bioaccumulation in the environment which may cause resistance to bacterial strains. The kinetic and mechanistic aspects of the photosensitized degradation of Amx and Cfx have been studied in water at pH 7.4 and 10 by stationary and time-resolved methods. Kinetic evidence indicates that the Rose Bengal-sensitized photooxidation of Amx at pH 7.4 proceeds via O(2)((1)Δ(g)) and O(2•-) mechanisms while at pH 10 the degradation path occurs, principally, via O(2)((1)Δ(g)). For Cfx, this process is attributed to O(2)((1)Δ(g)) and O(2•-). Photoproducts, which arise from the addition of oxygen atoms and subsequent oxidation of the groups -CH(3) to -COOH, were detected. For both antibiotics the bacteriostatic activity decreases in parallel to their photodegradation. The results of this study could potentially help scientists to better understand and predict the photodegradability of these antibiotics on living organisms and in different environmental compartments.

Photocatalytic oxidation of tabun simulant-diethyl cyanophosphate: FTIR in situ investigation.

PubMed

Kolinko, P A; Kozlov, D V

2008-06-15

Gas phase photocatalytic oxidation of diethyl cyanophosphate vapor in a static reactor using TiO2 and modified TiO2 as the photocatalyst was studied with the FTIR in situ method. The transition metals Pt, Au, and Ag were used for TiO2 modification by the chemical and photochemical deposition methods as well as the mechanical mixture of TiO2 with manganese oxide to improve its adsorption and catalytic activity. Photocatalytic oxidation of diethyl cyanophosphate in a static reactor results in its complete mineralization with carbon dioxide, phosphoric and nitric acids, and water as the major final products. HCN was demonstrated to be the only toxic gaseous intermediate of diethyl cyanophosphate photocatalytic oxidation, formed as a result of diethyl cyanophosphate hydrolysis. Diethylphosphate and acetic and formic acids were registered as the surface intermediates. It was found that cyanhydric acid is oxidized slowly with the use of unmodified TiO2. The formation of surface cyanide complexes with Ag and Au ions could be responsible for the fast removal of HCN from the gas phase and its further photooxidation in the case of using TiO2 with deposited Au and Ag.

Roles of reactive oxygen species in UVA-induced oxidation of 5,6-dihydroxyindole-2-carboxylic acid-melanin as studied by differential spectrophotometric method.

PubMed

Ito, Shosuke; Kikuta, Marina; Koike, Shota; Szewczyk, Grzegorz; Sarna, Michal; Zadlo, Andrzej; Sarna, Tadeusz; Wakamatsu, Kazumasa

2016-05-01

Eumelanin photoprotects pigmented tissues from ultraviolet (UV) damage. However, UVA-induced tanning seems to result from the photooxidation of preexisting melanin and does not contribute to photoprotection. We investigated the mechanism of UVA-induced degradation of 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-melanin taking advantage of its solubility in a neutral buffer and using a differential spectrophotometric method to detect subtle changes in its structure. Our methodology is suitable for examining the effects of various agents that interact with reactive oxygen species (ROS) to determine how ROS is involved in the UVA-induced oxidative modifications. The results show that UVA radiation induces the oxidation of DHICA to indole-5,6-quinone-2-carboxylic acid in eumelanin, which is then cleaved to form a photodegraded, pyrrolic moiety and finally to form free pyrrole-2,3,5-tricarboxylic acid. The possible involvement of superoxide radical and singlet oxygen in the oxidation was suggested. The generation and quenching of singlet oxygen by DHICA-melanin was confirmed by direct measurements of singlet oxygen phosphorescence. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Genetic manipulation of carotenoid biosynthesis and photoprotection.

PubMed

Pogson, B J; Rissler, H M

2000-10-29

There are multiple complementary and redundant mechanisms to provide protection against photo-oxidative damage, including non-photochemical quenching (NPQ). NPQ dissipates excess excitation energy as heat by using xanthophylls in combination with changes to the light-harvesting complex (LHC) antenna. The xanthophylls are oxygenated carotenoids that in addition to contributing to NPQ can quench singlet or triplet chlorophyll and are necessary for the assembly and stability of the antenna. We have genetically manipulated the expression of the epsilon-cyclase and beta-carotene hydroxylase carotenoid biosynthetic enzymes in Arabidopsis thaliana. The epsilon-cyclase overexpression confirmed that lut2 (lutein deficient) is a mutation in the epsilon-cyclase gene and demonstrated that lutein content can be altered at the level of mRNA abundance with levels ranging from 0 to 180% of wild-type. Also, it is clear that lutein affects the induction and extent of NPQ. The deleterious effects of lutein deficiency on NPQ in Arabidopsis and Chlamydomonas are additive, no matter what the genetic background, whether npq1 (zeaxanthin deficient), aba1 or antisense beta-hydroxylase (xanthophyll cycle pool decreased). Additionally, increasing lutein content causes a marginal, but significant, increase in the rate of induction of NPQ despite a reduction in the xanthophyll cycle pool size.

Genetic manipulation of carotenoid biosynthesis and photoprotection.

PubMed Central

Pogson, B J; Rissler, H M

2000-01-01

There are multiple complementary and redundant mechanisms to provide protection against photo-oxidative damage, including non-photochemical quenching (NPQ). NPQ dissipates excess excitation energy as heat by using xanthophylls in combination with changes to the light-harvesting complex (LHC) antenna. The xanthophylls are oxygenated carotenoids that in addition to contributing to NPQ can quench singlet or triplet chlorophyll and are necessary for the assembly and stability of the antenna. We have genetically manipulated the expression of the epsilon-cyclase and beta-carotene hydroxylase carotenoid biosynthetic enzymes in Arabidopsis thaliana. The epsilon-cyclase overexpression confirmed that lut2 (lutein deficient) is a mutation in the epsilon-cyclase gene and demonstrated that lutein content can be altered at the level of mRNA abundance with levels ranging from 0 to 180% of wild-type. Also, it is clear that lutein affects the induction and extent of NPQ. The deleterious effects of lutein deficiency on NPQ in Arabidopsis and Chlamydomonas are additive, no matter what the genetic background, whether npq1 (zeaxanthin deficient), aba1 or antisense beta-hydroxylase (xanthophyll cycle pool decreased). Additionally, increasing lutein content causes a marginal, but significant, increase in the rate of induction of NPQ despite a reduction in the xanthophyll cycle pool size. PMID:11127994

Photodynamic therapy--mechanism and employment.

PubMed

Szpringer, Ewa; Lutnicki, Krzysztof; Marciniak, Andrzej

2004-01-01

Photodynamic terapy (PDT) is a new treatment for a wide variety of malignancies and premalignant dysplasias, as well as some non-cancer indications. Therapeutic response to PTD is achieved through the activation of non-toxic photosensitiser located within neoplastic tissue, using visible light tuned to the appropriate absorption band of the photosensitiser molecule. This produces cytotoxic free radical such as singlet oxigen, which result in local photo-oxidation, cell damage and destruction of the tumour cells. Systemic administration of photosensitisers has been used with endoscopic light exposure to treat a variety of internal malignances. A topical drug delivery is used in the skin deseases treatment. The selective distribution of photosensitiser in the target tissue is the fundamental to the process of PDT. This tissue specific photosensitation and normal tissue sparing results in good healing and often very good cosmetic results. Peterson PTD can be used for the treatment of cutaneous lesions (e.g., SCC, BCC, Bowen's disease, mycosis fungoides, erythroplasia of Queyrat, Gorlin's Syndrome, actinic keratoses), lower genital tract neoplasia (VIN and CIN), gastrointestinal tumours, etc., as well as nononcological indications (e.g., acne, condyloma acuminatum, lichen planus, psoriasis, vitiligo, vulval lichen sclerosus, warts and verrucae).

Fluorescent excitation of Fe 2, Mn 2, Ti 2, N 1 lines by V 4, N 5, O 6: Emission lines in the spectra of symbiotic stars and Seyfert galaxies

NASA Technical Reports Server (NTRS)

Gilra, D. P.

1984-01-01

Analysis of the published IUE and ground based high resolution spectra of symbiotic stars, particularly RR Tel, shows that the dominant excitation mechanism of Fe II, Mn II, Ti II, and N I lines is the selective fluorescent excitation of some levels by the strong C IV, N V, and O VI emission lines. The same mechanism should work for the excitation of Fe II lines in the spectra of Seyfert galaxies and Q60's whose emission spectra are quite similar to those of symbiotic stars. The similarities and differences between the fluroescent excitation mechanism reported herein and the Bowen's mechanism is analyzed.

Mechanisms of electron transfer from structrual Fe(II) in reduced nontronite to oxygen for production of hydroxyl radicals

NASA Astrophysics Data System (ADS)

Yuan, Songhu; Liu, Xixiang; Liao, Wenjuan; Zhang, Peng; Wang, Xiaoming; Tong, Man

2018-02-01

Production of hydroxyl radicals (radOH) has been recently revealed upon oxygenation of sediments in redox-dynamic subsurface environments. In particular, Fe(II)-bearing clay minerals are the major sediment components contributing to radOH production upon oxygenation, and the produced radOH can oxidize contaminants and inactivate bacteria. Whereas, the mechanisms of radOH production from oxygenation of Fe(II)-bearing clay minerals remain elusive. The objectives of this study were to identify the structural variation of Fe(II) entities during the oxidation of Fe(II)-bearing clay minerals by O2, and to unravel the mechanisms of electron transfer within the mineral structure and from mineral to O2 for radOH production. Nontronite (NAu-2, 23% Fe) which was chemically reduced to 54.5% Fe(II) in total Fe was used as a model Fe(II)-bearing clay mineral. Production of radOH and oxidation of Fe(II) were measured during the oxidation of reduced NAu-2 by O2. A wide spectrum of spectroscopic techniques, including Fourier transform infrared spectroscopy (FTIR), Fe K-edge X-ray absorption spectroscopy (XAS), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS), were employed to explore the structural variation of Fe(II) entities in NAu-2 and the electron transfer within NAu-2 and from NAu-2 to O2. For 180 min oxidation of 1 g/L reduced NAu-2, a biphasic radOH production was observed, being quick within the initial 15 min and slow afterwards. Production of radOH correlates well with oxidation of Fe(II) in the reduced NAu-2. Within the initial 15 min, trioctahedral Fe(II)-Fe(II)-Fe(II) entities and edge Fe(II) in the reduced NAu-2 were preferentially and quickly oxidized, and electrons from the interior Fe(II)-Fe(II)-Fe(II) entities were most likely ejected from the basal siloxane plane to O2. Meanwhile, trioctahedral Fe(II)-Fe(II)-Fe(II) entities were mainly transformed to dioctahedral Fe(II)-Fe(II) entities. When the time of oxygenation was longer than 15 min, dioctahedral Al-Fe(II), Fe(II)-Fe(II) and Fe(II)-Fe(III) entities were slowly oxidized, and the interior electrons were transported through Fe(II)-O-Fe(III) linkages to edges and then ejected to O2. In the slow stage of oxidation, electrons from interior Fe(II) accumulated towards the near surface layers and fueled the regeneration of edge Fe(II) for radOH production. In both stages, one-electron transfer mechanism with the involvement of O2rad - and H2O2 applies for radOH production from the oxidation of structural Fe(II) by O2. The mechanisms unraveled in this study advance the understanding of reactive oxygen species (ROS) production and structural Fe variation when Fe(II)-bearing clay minerals are oxygenated in redox-dynamic systems.

Spectroscopic evidence for the role of a site of the di-iron catalytic center of ferritins in tuning the kinetics of Fe(ii) oxidation.

PubMed

Ebrahimi, Kourosh Honarmand; Bill, Eckhard; Hagedoorn, Peter-Leon; Hagen, Wilfred R

2016-11-15

Ferritin is a nanocage protein made of 24 subunits. Its major role is to manage intracellular concentrations of free Fe(ii) and Fe(iii) ions, which is pivotal for iron homeostasis across all domains of life. This function of the protein is regulated by a conserved di-iron catalytic center and has been the subject of extensive studies over the past 50 years. Yet, it has not been fully understood how Fe(ii) is oxidized in the di-iron catalytic center and it is not known why eukaryotic and microbial ferritins oxidize Fe(ii) with different kinetics. In an attempt to obtain a new insight into the mechanism of Fe(ii) oxidation and understand the origin of the observed differences in the catalysis of Fe(ii) oxidation among ferritins we studied and compared the mechanism of Fe(ii) oxidation in the eukaryotic human H-type ferritin (HuHF) and the archaeal ferritin from Pyrococcus furiosus (PfFtn). The results show that the spectroscopic characteristics of the intermediate of Fe(ii) oxidation and the Fe(iii)-products are the same in these two ferritins supporting the proposal of unity in the mechanism of Fe(ii) oxidation among eukaryotic and microbial ferritins. Moreover, we observed that a site in the di-iron catalytic center controls the distribution of Fe(ii) among subunits of HuHF and PfFtn differently. This observation explains the reported differences between HuHF and PfFtn in the kinetics of Fe(ii) oxidation and the amount of O 2 consumed per Fe(ii) oxidized. These results provide a fresh understanding of the mechanism of Fe(ii) oxidation by ferritins.

Manganese inhibition of microbial iron reduction in anaerobic sediments

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1988-01-01

Potential mechanisms for the lack of Fe(II) accumulation in Mn(IV)-containing anaerobic sediments were investigated. The addition of Mn(IV) to sediments in which Fe(II) reduction was the terminal electron-accepting process removed all the pore-water Fe(II), completely inhibited net Fe(III) reduction, and stimulated Mn(IV) reduction. Results demonstrate that preferential reduction of Mn(IV) by FE(III)-reducing bacteria cannot completely explain the lack of Fe(II) accumulation in anaerobic, Mn(IV)-containing sediments, and indicate that Mn(IV) oxidation of Fe(II) is the mechanism that ultimately prevents Fe(II) accumulation. -Authors

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

DOE PAGES

Ho, Junming; Kish, Elizabeth; Méndez-Hernandez, Dalvin D.; ...

2017-06-26

In photosynthetic organisms, protection against photo-oxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll to carotenoid triplet-triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, while it is ultrafast in the oxygen-rich chloroplasts of oxygen evolving photosynthetic organisms. In order to better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomericmore » carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET including a resonance Raman based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by DFT calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). In conclusion, both DFT and EPR analysis further indicates that upon T-TET, the triplet wave function is localized on the carotenoid in both dyads.« less

Fluorescent proteins as singlet oxygen photosensitizers: mechanistic studies in photodynamic inactivation of bacteria

NASA Astrophysics Data System (ADS)

Ruiz-González, Rubén.; White, John H.; Cortajarena, Aitziber L.; Agut, Montserrat; Nonell, Santi; Flors, Cristina

2013-02-01

Antimicrobial photodynamic therapy (aPDT) combines a photosensitizer, light and oxygen to produce reactive oxygen species (ROS), mainly singlet oxygen (1O2), to photo-oxidize important biomolecules and induce cell death. aPDT is a promising alternative to standard antimicrobial strategies, but its mechanisms of action are not well understood. One of the reasons for that is the lack of control of the photosensitizing drugs location. Here we report the use of geneticallyencoded fluorescent proteins that are also 1O2 photosensitizers to address the latter issue. First, we have chosen the red fluorescent protein TagRFP as a photosensitizer, which unlike other fluorescent proteins such as KillerRed, is able to produce 1O2 but not other ROS. TagRFP photosensitizes 1O2 with a small, but not negligible, quantum yield. In addition, we have used miniSOG, a more efficient 1O2 photosensitizing fluorescent flavoprotein that has been recently engineered from phototropin 2. We have genetically incorporated these two photosensitizers into the cytosol of E. coli and demonstrated that intracellular 1O2 is sufficient to kill bacteria. Additional assays have provided further insight into the mechanism of cell death. Photodamage seems to occur primarily in the inner membrane, and extends to the outer membrane if the photosensitizer's efficiency is high enough. These observations are markedly different to those reported for external photosensitizers, suggesting that the site where 1O2 is primarily generated proves crucial for inflicting different types of cell damage.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2012-01-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

UVA Light-excited Kynurenines Oxidize Ascorbate and Modify Lens Proteins through the Formation of Advanced Glycation End Products

PubMed Central

Linetsky, Mikhail; Raghavan, Cibin T.; Johar, Kaid; Fan, Xingjun; Monnier, Vincent M.; Vasavada, Abhay R.; Nagaraj, Ram H.

2014-01-01

Advanced glycation end products (AGEs) contribute to lens protein pigmentation and cross-linking during aging and cataract formation. In vitro experiments have shown that ascorbate (ASC) oxidation products can form AGEs in proteins. However, the mechanisms of ASC oxidation and AGE formation in the human lens are poorly understood. Kynurenines are tryptophan oxidation products produced from the indoleamine 2,3-dioxygenase (IDO)-mediated kynurenine pathway and are present in the human lens. This study investigated the ability of UVA light-excited kynurenines to photooxidize ASC and to form AGEs in lens proteins. UVA light-excited kynurenines in both free and protein-bound forms rapidly oxidized ASC, and such oxidation occurred even in the absence of oxygen. High levels of GSH inhibited but did not completely block ASC oxidation. Upon UVA irradiation, pigmented proteins from human cataractous lenses also oxidized ASC. When exposed to UVA light (320–400 nm, 100 milliwatts/cm2, 45 min to 2 h), young human lenses (20–36 years), which contain high levels of free kynurenines, lost a significant portion of their ASC content and accumulated AGEs. A similar formation of AGEs was observed in UVA-irradiated lenses from human IDO/human sodium-dependent vitamin C transporter-2 mice, which contain high levels of kynurenines and ASC. Our data suggest that kynurenine-mediated ASC oxidation followed by AGE formation may be an important mechanism for lens aging and the development of senile cataracts in humans. PMID:24798334

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Junming; Kish, Elizabeth; Méndez-Hernandez, Dalvin D.

In photosynthetic organisms, protection against photo-oxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll to carotenoid triplet-triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, while it is ultrafast in the oxygen-rich chloroplasts of oxygen evolving photosynthetic organisms. In order to better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomericmore » carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET including a resonance Raman based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by DFT calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). In conclusion, both DFT and EPR analysis further indicates that upon T-TET, the triplet wave function is localized on the carotenoid in both dyads.« less

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

PubMed Central

Ho, Junming; Kish, Elizabeth; Méndez-Hernández, Dalvin D.; WongCarter, Katherine; Pillai, Smitha; Kodis, Gerdenis; Niklas, Jens; Poluektov, Oleg G.; Gust, Devens; Moore, Thomas A.; Moore, Ana L.; Batista, Victor S.

2017-01-01

In photosynthetic organisms, protection against photooxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll-to-carotenoid triplet–triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, whereas it is ultrafast in the oxygen-rich chloroplasts of oxygen-evolving photosynthetic organisms. To better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomeric carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET, including a resonance Raman-based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by density functional theory (DFT) calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light-harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). Both DFT and electron paramagnetic resonance (EPR) analyses further indicate that, upon T-TET, the triplet wave function is localized on the carotenoid in both dyads. PMID:28652359

Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

PubMed

Futera, Zdeněk; Burda, Jaroslav V

2014-07-15

Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA. Copyright © 2014 Wiley Periodicals, Inc.

Dissociation of I II in chemical oxygen-iodine lasers: experiment, modeling, and pre-dissociation by electrical discharge

NASA Astrophysics Data System (ADS)

Katz, A.; Waichman, K.; Dahan, Z.; Rybalkin, V.; Barmashenko, B. D.; Rosenwaks, S.

2007-06-01

The dissociation of I II molecules at the optical axis of a supersonic chemical oxygen-iodine laser (COIL) was studied via detailed measurements and three dimensional computational fluid dynamics calculations. Comparing the measurements and the calculations enabled critical examination of previously proposed dissociation mechanisms and suggestion of a mechanism consistent with the experimental and theoretical results obtained in a supersonic COIL for the gain, temperature and I II dissociation fraction at the optical axis. The suggested mechanism combines the recent scheme of Azyazov and Heaven (AIAA J. 44, 1593 (2006)), where I II(A' 3Π 2u), I II(A 3Π 1u) and O II(a1Δ g, v) are significant dissociation intermediates, with the "standard" chain branching mechanism of Heidner et al. (J. Phys. Chem. 87, 2348 (1983)), involving I(2P 1/2) and I II(X1Σ + g, v). In addition, we examined a new method for enhancement of the gain and power in a COIL by applying DC corona/glow discharge in the transonic section of the secondary flow in the supersonic nozzle, dissociating I II prior to its mixing with O II(1Δ). The loss of O II(1Δ) consumed for dissociation was thus reduced and the consequent dissociation rate downstream of the discharge increased, resulting in up to 80% power enhancement. The implication of this method for COILs operating beyond the specific conditions reported here is assessed.

Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

NASA Astrophysics Data System (ADS)

MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

2014-12-01

Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

Spectral analysis of fundus autofluorescence pattern as a tool to detect early stages of degeneration in the retina and retinal pigment epithelium.

PubMed

Feldman, Tatiana B; Yakovleva, Marina A; Larichev, Andrey V; Arbukhanova, Patimat M; Radchenko, Alexandra Sh; Borzenok, Sergey A; Kuzmin, Vladimir A; Ostrovsky, Mikhail A

2018-05-22

The aim of this work is the determination of quantitative diagnostic criteria based on the spectral characteristics of fundus autofluorescence to detect early stages of degeneration in the retina and retinal pigment epithelium (RPE). RPE cell suspension samples were obtained from the cadaver eyes with and without signs of age-related macular degeneration (AMD). Fluorescence analysis at an excitation wavelength of 488 nm was performed. The fluorescence lifetimes of lipofuscin-granule fluorophores were measured by counting time-correlated photon method. Comparative analysis of fluorescence spectra of RPE cell suspensions from the cadaver eyes with and without signs of AMD showed a significant difference in fluorescence intensity at 530-580 nm in response to fluorescence excitation at 488 nm. It was notably higher in eyes with visual pathology than in normal eyes regardless of the age of the eye donor. Measurements of fluorescence lifetimes of lipofuscin fluorophores showed that the contribution of photooxidation and photodegradation products of bisretinoids to the total fluorescence at 530-580 nm of RPE cell suspensions was greater in eyes with visual pathology than in normal eyes. Because photooxidation and photodegradation products of bisretinoids are markers of photodestructive processes, which can cause RPE cell death and initiate degenerative processes in the retina, quantitative determination of increases in these bisretinoid products in lipofuscin granules may be used to establish quantitative diagnostic criteria for degenerative processes in the retina and RPE.

The specific interaction of the photosensitizer methylene blue with acetylcholinesterase provides a model system for studying the molecular consequences of photodynamic therapy.

PubMed

Silman, Israel; Roth, Esther; Paz, Aviv; Triquigneaux, Mathilde M; Ehrenshaft, Marilyn; Xu, Yechun; Shnyrov, Valery L; Sussman, Joel L; Deterding, Leesa J; Ashani, Yacov; Mason, Ronald P; Weiner, Lev

2013-03-25

The photosensitizer, methylene blue (MB), generates singlet oxygen ((1)O2) that irreversibly inhibits Torpedo californica acetylcholinesterase (TcAChE). In the dark MB inhibits reversibly, binding being accompanied by a bathochromic shift that can be used to show its displacement by other reversible inhibitors binding to the catalytic 'anionic' subsite (CAS), the peripheral 'anionic' subsite (PAS), or bridging them. Data concerning both reversible and irreversible inhibition are here reviewed. MB protects TcAChE from thermal denaturation, and differential scanning calorimetry reveals a ~8 °C increase in the denaturation temperature. The crystal structure of the MB/TcAChE complex reveals a single MB stacked against W279 in the PAS, pointing down the gorge towards the CAS. The intrinsic fluorescence of the irreversibly inhibited enzyme displays new emission bands that can be ascribed to N'-formylkynurenine (NFK); this was indeed confirmed using anti-NFK antibodies. Mass spectroscopy revealed that two Trp residues, Trp84 in the CAS, and Trp279 in the PAS, were the only Trp residues, out of a total of 14, significantly modified by photo-oxidation, both being converted to NFK. In the presence of competitive inhibitors that displace MB from the gorge, their modification is completely prevented. Thus, photo-oxidative damage caused by MB involves targeted release of (1)O2 by the bound photosensitizer within the aqueous milieu of the active-site gorge. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Isoprene photochemistry over the Amazon rainforest.

PubMed

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Isoprene photochemistry over the Amazon rainforest

NASA Astrophysics Data System (ADS)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.; Martin, Scot T.

2016-05-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Role of Fe doping in tuning the band gap of TiO2 for photo-oxidation induced cytotoxicity paradigm

PubMed Central

George, Saji; Pokhrel, Suman; Ji, Zhaoxia; Henderson, Bryana L.; Xia, Tian; Li, LinJiang; Zink, Jeffrey I.; Nel, André E.; Mädler, Lutz

2014-01-01

UV-Light induced electron-hole (e−/h+) pair generation and free radical production in TiO2 based nanoparticles is a major conceptual paradigm for biological injury. However, to date, this hypothesis has been difficult to experimentally verify due to the high energy of UV light that is intrinsically highly toxic to biological systems. Here, a versatile flame spray pyrolysis (FSP) synthetic process has been exploited to synthesize a library of iron doped (0–10 at wt%) TiO2 nanoparticles. These particles have been tested for photoactivation-mediated cytotoxicity using near-visible light exposure. The reduction in TiO2 band gap energy with incremental levels of Fe loading maintained the nanoparticle crystalline structure in spite of homogeneous Fe distribution (demonstrated by XRD, HRTEM, SAED, EFTEM, and EELS). Photochemical studies showed that band gap energy was reciprocally tuned proportional to the Fe content. The photo-oxidation capability of Fe-doped TiO2 was found to increase during near-visible light exposure. Use of a macrophage cell line to evaluate cytotoxic and ROS production showed increased oxidant injury and cell death in parallel with a decrease in band gap energy. These findings demonstrate the importance of band gap energy in the phototoxic response of the cell to TiO2 nanoparticles and reflect the potential of this material to generate adverse effects in humans and the environment during high intensity light exposure. PMID:21678906

Mapping three guanine oxidation products along DNA following exposure to three types of reactive oxygen species.

PubMed

Matter, Brock; Seiler, Christopher L; Murphy, Kristopher; Ming, Xun; Zhao, Jianwei; Lindgren, Bruce; Jones, Roger; Tretyakova, Natalia

2018-06-01

Reactive oxygen and nitrogen species generated during respiration, inflammation, and immune response can damage cellular DNA, contributing to aging, cancer, and neurodegeneration. The ability of oxidized DNA bases to interfere with DNA replication and transcription is strongly influenced by their chemical structures and locations within the genome. In the present work, we examined the influence of local DNA sequence context, DNA secondary structure, and oxidant identity on the efficiency and the chemistry of guanine oxidation in the context of the Kras protooncogene. A novel isotope labeling strategy developed in our laboratory was used to accurately map the formation of 2,2-diamino-4-[(2-deoxy-β-D-erythropentofuranosyl)amino]- 5(2 H)-oxazolone (Z), 8-oxo-7,8-dihydro-2'-deoxyguanosine (OG), and 8-nitroguanine (8-NO 2 -G) lesions along DNA duplexes following photooxidation in the presence of riboflavin, treatment with nitrosoperoxycarbonate, and oxidation in the presence of hydroxyl radicals. Riboflavin-mediated photooxidation preferentially induced OG lesions at 5' guanines within GG repeats, while treatment with nitrosoperoxycarbonate targeted 3'-guanines within GG and AG dinucleotides. Little sequence selectivity was observed following hydroxyl radical-mediated oxidation. However, Z and 8-NO 2 -G adducts were overproduced at duplex ends, irrespective of oxidant identity. Overall, our results indicate that the patterns of Z, OG, and 8-NO 2 -G adduct formation in the genome are distinct and are influenced by oxidant identity and the secondary structure of DNA. Copyright © 2018 Elsevier Inc. All rights reserved.

Features of the supercritical CO2-assisted immobilization of fluorinated tetraphenylporphyrins into tetrafluoroethylene copolymers

NASA Astrophysics Data System (ADS)

Shershnev, I. V.; Cherkasova, A. V.; Kopylov, A. S.; Glagolev, N. N.; Bragina, N. A.; Solov'eva, A. B.

2017-07-01

The immobilization of fluorinated tetraphenylporphyrins (FTPPs) into tetrafluoroethylene copolymers (fluoroplast F-42 and MF-4SK, a perfluorinated sulfonic acid cation exchanger in H+-form) is conducted in supercritical CO2 (scCO2). The effects the conditions of immobilization (the temperature and pressure of scCO2, reaction time, and the addition of cosolvents) and the structure of the carrier polymer have on the content of porphyrin in these polymers is studied. The porphyrin-loaded polymer systems are shown to exhibit photosensitizing activity in anthracene and cholesterol oxidation in scCO2. Under conditions of photocatalysis, chemical and functional stability is a feature of only MF-4SK polymer systems; this is attributed to the formation of protonated forms of the porphyrins and their interaction with SO3 --groups of the polymer (an ion exchange process), which prevents leaching of the FTPP from the polymer matrix. The photocatalytic process actually occurs inside the matrix of the perfluorinated copolymer, with the protonated form of the porphyrin acting as a photosensitizer. The rate constant of anthracene photooxidation in the presence of FTPP-loaded MF-4SK films in scCO2 is found to pass through a maximum as a function of the porphyrin content and the polymer film thickness. The use of such catalytic systems for cholesterol photooxidation in scCO2 is shown to produce a virtual monoproduct (yield, 10%): 6-formyl-B-norcholestane-3,5-diol, a compound with high biological activity.

Slow photon amplification of gas-phase ethanol photo-oxidation in titania inverse opal photonic crystals

NASA Astrophysics Data System (ADS)

Jovic, Vedran; Idriss, Hicham; Waterhouse, Geoffrey I. N.

2016-11-01

Here we describe the successful fabrication of six titania inverse opal (TiO2 IO) photocatalysts with fcc[1 1 1] pseudo photonic band gaps (PBGs) tuned to span the UV-vis region. Photocatalysts were fabricated by a colloidal crystal templating and sol-gel approach - a robust and highly applicable bottom-up scheme which allowed for precise control over the geometric and optical properties of the TiO2 IO photocatalysts. Optical properties of the TiO2 IO thin films were investigated in detail by UV-vis transmittance and reflectance measurements. The PBG along the fcc[1 1 1] direction in the TiO2 IOs was dependent on the inter-planar spacing in the [1 1 1] direction, the incident angle of light and the refractive index of the medium filling the macropores in the IOs, in agreement with a modified Bragg's law expression. Calculated photonic band structures for the photocatalysts revealed a PBG along the Γ → L direction at a/λ ∼ 0.74, in agreement with the experimental optical data. By coupling the low frequency edge of the PBG along the [1 1 1] direction with the electronic absorption edge of anatase TiO2, a two-fold enhancement in the rate of gas phase ethanol photo-oxidation in air was achieved. This enhancement appears to be associated with a 'slow photon' effect that acts to both enhance TiO2 absorption and inhibit spontaneous emission (i.e. suppress electron-hole pair recombination).

Melanin may promote photooxidation of linoleic acid

NASA Astrophysics Data System (ADS)

Glickman, Randolph D.; Lam, Kwok-Wai

1995-05-01

We have previously shown that laser-exposed melanin granules isolated from the retinal pigment epithelium (RPE) are capable of oxidizing ascorbic acid. We are now characterizing the reactions of light- activated melanin with other cellular components such as linoleic acid, a polyunsaturated fatty acid. Commercial linoleic acid, and melanin granules isolated from bovine RPE cells, are mixed and exposed to the broad band output of a 150 W Xenon arc lamp or the CW output of an Argon laser. Native linoleic acid is separated from its hydroperoxides by HPLC, and the relative amounts of each are detected by UV absorbance at 210 and 232 nm, respectively. Exposure of the linoleic acid alone to the xenon arc source results in production of linoleic hydroperoxides (LHP) in an intensity-dependent reaction that doubles in extent over the temperature range of 0° to 80°C. Addition of melanin granules at a density of 108 granules/ml reduces the production of LHP, probably because of light absorption and self-screening by the melanin. At or below a density of 107 granules/ml, however, the light-driven production of LHP is enhanced, especially during exposure to the blue- green output of the Argon laser. Physiological antioxidants (Vit. C,E protect the linoleic acid from photo-oxidation in the presence or absence of melanin. These observations support the hypothesis that light-activated melanin can react with some cellular components and thereby contribute to photochemical damage, especially if endogenous antioxidants are depleted.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.