Structure-Dependent Photodegradation of Carotenoids Accelerated by Dimethyl Tetrasulfide under UVA Irradiation

Carotenoids are used in wide-ranging food applications, but they are susceptible to degradation by many factors including light. We examined the photodegradation of five kinds of carotenoids and three kinds of anthocyanins to clarify which structures of pigments were favorable to accelerated degradation by sulfides under UVA irradiation. Under UVA irradiation, crocetin and crocin were decomposed more rapidly in the presence of dimethyl tetrasulfide than in the absence of the sulfide, but not as rapidly as β-carotene, zeaxanthin and β-cryptoxanthin were. However, cyanidin was decomposed more slowly in the presence of sulfide than in the absence of sulfide. Moreover, the photodegradation of kuromanin and keracyanin was not affected by the addition of a sulfide. We also examined the mechanism for this accelerated degradation. Normal hexane was more favorable to the photodegradation of β-carotene than methanol and ethanol. The accelerated degradation was inhibited by free radical scavengers, but enhanced by the addition of deuterium oxide. These results suggest that conjugated double bonds were favorable to the accelerated photodegradation by sulfide and that this reaction was mediated by free radicals.     

Litter Decomposition in a California Annual Grassland: Interactions Between Photodegradation and Litter Layer Thickness

In annual grasslands that experience a mediterranean-type climate, the synchrony between plant senescence and peak solar radiation over summer results in high litter sun exposure. We examined the decomposition of both shaded and sun-exposed litter over summer and inferred the effects of photodegradation from changes in mass loss and litter chemistry. The carry-over effects of summer litter exposure on wet season decomposition were also assessed, and the attenuation of photodegradation with litter layer thickness was used to estimate the proportion of grass litter lignin susceptible to photodegradation under different treatments of a factorial global change experiment. Over summer, mass loss from grass and forb litter exposed to ambient sunlight ranged from 8% to 10%, whereas lignin decreased in grass litter by approximately 20%. After one year of decomposition, mass losses from grass leaves exposed to sunlight over summer were more than double the mass losses from summer-shaded leaves. When shade litter layer thickness was varied, mass losses over summer for all treatments were also approximately 8%; however, lignin decreased significantly only in the low shade treatments (0–64 g m⁻² of shade litter). Aboveground production of annual grasses nearly quadrupled in response to the combined effects of N addition, elevated atmospheric CO₂, increased precipitation and warming. The estimated proportion of grass litter lignin experiencing full photodegradation ranged from 100% under ambient conditions to 31–62% in plots receiving the combined global change treatments. These results reveal an important role of sun exposure over summer in accelerating litter decomposition in these grasslands and provide evidence that future changes in the quantity of litter deposition may modulate the influence of photodegradation integrated across the litter layer.     

Widespread production of nonmicrobial greenhouse gases in soils

Carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) are the three most important greenhouse gases (GHGs), and all show large uncertainties in their atmospheric budgets. Soils of natural and managed ecosystems play an extremely important role in modulating their atmospheric abundance. Mechanisms underlying the exchange of these GHGs at the soil–atmosphere interface are often assumed to be exclusively microbe‐mediated (M‐GHGs). We argue that it is a widespread phenomenon for soil systems to produce GHGs through nonmicrobial pathways (NM‐GHGs) based on a review of the available evidence accumulated over the past half century. We find that five categories of mechanistic process, including photodegradation, thermal degradation, reactive oxidative species (ROS) oxidation, extracellular oxidative metabolism (EXOMET), and inorganic chemical reactions, can be identified as accounting for their production. These pathways are intricately coupled among themselves and with M‐GHGs production and are subject to strong influences from regional and global change agents including, among others, climate warming, solar radiation, and alterations of atmospheric components. Preliminary estimates have suggested that NM‐GHGs could play key roles in contributing to budgets of GHGs in the arid regions, whereas their global importance would be enhanced with accelerated global environmental changes. Therefore, more research should be undertaken, with a differentiation between NM‐GHGs and M‐GHGs, to further elucidate the underlying mechanisms, to investigate the impacts of various global change agents, and to quantify their contributions to regional and global GHGs budgets. These efforts will contribute to a more complete understanding of global carbon and nitrogen cycling and a reduction in the uncertainty of carbon‐climate feedbacks in the Earth system.     

Substitution of Lysine for Arginine in the N-Terminal 217th Amino Acid Residue of the HγII of Staphylococcall γ-Hemolysin Lowers the Activity of the Toxin

The staphyloccocal toxin γ-hemolysin consists of two protein components, LukF and HyII. Staphylococcus aureus P83 was found to have five components, LukF, LukF-PV, LukM, LukS, and HγII for leukocidin or γ-hemolysin. HγII of S. aureus P83 was demonstrated to be a naturally-occurring analogous molecule of HγII [HγII(P83)], in which the 217th arginine residue was replaced by lysine. The HγII(P83) showed about 50% of the hemolytic activity of normal HyII in the presence of LukF.     

TRANSFORMATION AND ALLELOPATHY OF NATURAL DISSOLVED ORGANIC CARBON AND TANNIC ACID ARE AFFECTED BY SOLAR RADIATION AND BACTERIA1

The aim of this study was to test whether abiotic and biotic factors may affect allelopathic properties. Therefore, we investigated how solar radiation and bacteria influence allelopathic effects of the plant‐derived, polyphenolic tannic acid (TA) on microalgae. Using a block design, lake water samples with and without TA were exposed to solar radiation or kept in darkness with or without bacteria for 3 weeks. Dissolved organic carbon (DOC), specific size fractions of DOC analyzed by chromatography–organic carbon detection (LC‐OCD), and concentrations of total phenolic compounds (TPC) were measured to follow the fate of TA in lake water with natural DOC exposed to photolytic and microbial degradation. DOC and TPC decreased in dark‐incubated lake water with TA and bacteria indicating microbial degradation. In contrast, exposure to solar radiation of lake water with TA and bacteria did not decrease DOC. Chromatographic analyses documented an accumulation of DOC mean size fraction designated as humic substances (HS) in sunlit water samples with TA. The recalcitrance of the humic fraction indicates that photolytic degradation may contribute to a DOC less available for bacterial degradation. Subsequent growth tests with Desmodesmus armatus (Chodat) E. Hegewald showed low but reproducible difference in algal growth with lower algal growth rate cultured in photolytically and microbially degraded TA in lake water than cultured in respective dark treatments. This finding highlights the importance of photolytic processes and microbial degradation influencing allelopathic effects and may explain the high potential of allelochemicals for structuring the phytoplankton community composition in naturally illuminated surface waters.     

Photochemical processes and the environmental impact of petroleum spills

A review of the photochemical processes involved in the degradation of petroleum,its products, and some model compounds found in petroleum. Emphasis is given to processes which affect emulsification, water solubility, and toxicity. Waterphase photodegradation is also treated. The interaction of these processes withbiodegradation is discussed. Areas requiring further work are indicated. 96references.     

Carbon Dangling Bonds in Photodegraded Polymer:Fullerene Solar Cells

Intrinsic photodegradation of organic solar cells, theoretically attributed to C? H bond rearrangement/breaking, remains a key commercialization barrier. This work presents, via dark electron paramagnetic resonance (EPR), the first experimental evidence for metastable C dangling bonds (DBs) formed by blue/UV irradiation of polymer:fullerene blend films in nitrogen. The DB density increases with irradiation and decreases ≈4‐fold after 2 weeks in the dark. The dark EPR also shows increased densities of other spin‐active sites in photodegraded polymer, fullerene, and polymer:fullerene blend films, consistent with broad electronic measurements of fundamental properties, including defect/gap state densities. The EPR and electronic measurements enable identification of defect states, whether in the polymer, fullerene, or at the donor/acceptor (D/A) interface. Importantly, the EPR results indicate that the DBs are at the D/A interface, as they were present only in the blend films. The role of polarons in interface DB formation is also discussed.     

Effect of Counterion on the Solid State Photodegradation Behavior of Prazosin Salts

The effect of counterion was evaluated on the photodegradation behavior of six prazosin salts, viz., prazosin hydrochloride anhydrous, prazosin hydrochloride polyhydrate, prazosin tosylate anhydrous, prazosin tosylate monohydrate, prazosin oxalate dihydrate, and prazosin camsylate anhydrous. The salts were subjected to UV–Visible irradiation in a photostability test chamber for 10 days. The samples were analyzed for chemical changes by a specific stability-indicating high-performance liquid chromatography method. pH of the microenvironment was determined in 10% w/v aqueous slurry of the salts. The observed order of photostability was: prazosin hydrochloride anhydrous > prazosin camsylate anhydrous ∼ prazosin-free base > prazosin hydrochloride polyhydrate > prazosin tosylate anhydrous > prazosin oxalate dihydrate ∼ prazosin tosylate monohydrate. Multivariate analysis of the photodegradation behavior suggested predominant contribution of the state of hydration and also intrinsic photosensitivity of the counterion. Overall, hydrated salts showed higher photodegradation compared to their anhydrous counterparts. Within the anhydrous salts, aromatic and carbonyl counterion-containing salts showed higher susceptibility to light. The pH of microenvironment furthermore contributed to photodegradation of prazosin salts, especially for drug counterions with inherent higher pH. The study reveals importance of selection of a suitable drug salt form for photosensitive drugs during preformulation stage of drug development.     

Morphology Related Photodegradation of Low‐Band‐Gap Polymer Blends

The morphology related photodegradation of low band‐gap polymer blends is investigated using optical microscopy and scanning probe microscopy. Poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothiadiazole)] (C‐PCPDTBT):[6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) blend films without and with ODT, as well as poly[(4,40‐bis(2‐ethylhexyl)dithieno[3,2‐b:20,30‐d]silole)‐2,6‐diylalt‐(2,1,3‐benzothiadiazole)‐4,7‐diyl] (Si‐PCPDTBT):PCBM blend films exposed to a focused 632.8 nm laser under ambient condition with and without inert gas protection are studied. The photodegradation of the polymer starts in the vicinity of the PCBM molecules (first sphere degradation), which effectively blocks the electron transfer processes. Stern‐Volmer type kinetics are observed in the C‐PCPDTBT:PCBM blend with ODT, which indicates that only a small number of photo‐oxidized monomer units act as quenchers of the C‐PCPDTBT polymer luminescence. Furthermore, in addition to the permanent damage of the polymer molecules, as witnessed from their Raman intensity decrease, the polymer photoluminescence demonstrates partial reversible recovery when inert gas protection is resumed, indicating the involvement of temporary polymer/O₂‐charge transfer complexes in the photodegradation process.