Photodegradation of carbon dots cause cytotoxicity.

Carbon dots (CDs) are photoluminescent nanomaterials with wide-ranging applications. Despite their photoactivity, it remains unknown whether CDs degrade under illumination and whether such photodegradation poses any cytotoxic effects. Here, we show laboratory-synthesized CDs irradiated with light degrade into molecules that are toxic to both normal (HEK-293) and cancerous (HeLa and HepG2) human cells. Eight days of irradiation photolyzes 28.6-59.8% of the CDs to <3 kilo Dalton molecules, 1431 of which are detected by high-throughput, non-target high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Molecular network and community analysis further reveal 499 cytotoxicity-related molecules, 212 of which contain polyethylene glycol, glucose, or benzene-related structures. Photo-induced production of hydroxyl and alkyl radicals play important roles in CD degradation as affected by temperature, pH, light intensity and wavelength. Commercial CDs show similar photodegraded products and cytotoxicity profiles, demonstrating that photodegradation-induced cytotoxicity is likely common to CDs regardless of their chemical composition. Our results highlight the importance of light in cytocompatibility studies of CDs.

Indirect Photodegradation of Sulfamethoxazole and Trimethoprim by Hydroxyl Radicals in Aquatic Environment: Mechanisms, Transformation Products and Eco-Toxicity Evaluation.

The bacteriostatic antibiotics, sulfamethoxazole (SMX) and trimethoprim (TMP), have frequently been found in wastewater and surface water, which raises the concerns about their ecotoxicological effects. The indirect photochemical transformation has been proven to be an efficient way to degrade SMX and TMP. In this study, the reaction mechanisms of the degradation by SMX and TMF by OH radicals were investigated by theoretical calculations. Corresponding rate constants were determined and the eco-toxicity of SMX and TMP and its degradations products were predicted using theoretical models. The results indicate that the most favorable pathways for the transformation of SMX and TMP are both •OH-addition reaction of benzene ring site with lowest Gibbs free energy barriers (6.86 and 6.21 kcal mol-1). It was found that the overall reaction rate constants of •OH-initial reaction of SMX and TMP are 1.28 × 108 M-1 s-1 and 6.21 × 108 M-1 s-1 at 298 K, respectively. When comparing the eco-toxicity of transformation products with parent SMX and TMP, it can be concluded that the acute and chronic toxicities of the degraded products are reduced, but some products remain harmful for organisms, especially for daphnid (toxic or very toxic level). This study can give greater insight into the degradation of SMX and TMP by •OH through theoretical calculations in aquatic environment.

Endothelial dysfunction induced by hydroxyl radicals - the hidden face of biodegradable Fe-based materials for coronary stents.

Fe-based materials are currently considered for manufacturing biodegradable coronary stents. Here we show that Fe has a strong potential to generate hydroxyl radicals (HO) during corrosion. This HO generation, but not corrosion, can be inhibited by catalase. Oxidative stress was observed (increased HO-1 expression) in aortic rings after direct exposure to Fe, but not in the presence of catalase or after indirect exposure. This oxidative stress response induced an uncoupling of eNOS in, and a consequent reduced NO production by endothelial cells exposed to Fe. In isolated rat aortic rings NO production was also reduced by HO generated during Fe corrosion, as indicated by the protective role of catalase. Finally, all these mechanisms contributed to impaired endothelium-dependent relaxation in aortic rings caused by HO generated during the direct contact with Fe. This deleterious impact of Fe corrosion on the endothelial function should be integrated when considering the use of biodegradable Fe-based alloys for vascular implants.

Comparative study on skin protection activity of polyphenol-rich extract and polysaccharide-rich extract from Sargassum vachellianum.

Seaweed polyphenols and polysaccharide plays a broad range of biological activity. The objective of the present study was to study and compare the skin protection activity of fucoidan rich polysaccharide extract (SPS) and polyphenol-rich extract (SPP) from the seaweed Sargassum vachellianum. The skin protection activity was analyzed based on their ability to scavenge free radicals such as hydrogen peroxide and hydroxyl radicals, UV absorption potential, tyrosinase inhibition, moisture preservation, and antibacterial activity. From the results, both SPP and SPS protects the skin from UV damage. SPP showed good free radical scavenging ability, antimicrobial activity against E.coli and S. aureus and effectively absorbed the UVB and UVA rays whereas SPS hardly absorbs the UVA and UVB rays and showed weak free radical scavenging ability and no antimicrobial activity. SPS showed considerable inhibition on tyrosinase (51.21%) and had better moisture absorption (52.1%) and retention (63.24%) abilities than SPP. The results specified that both SPS and SPP have balancing potential on skin protection and suitable combinations of both could act as an active ingredient in cosmetics.

Antigenotoxic and antioxidant potential of medicinal mushrooms (Immune Assist) against DNA damage induced by free radicals-an in vitro study.

Immune Assist (IA) is produced from extract of six species of medical mushrooms: Agaricus blazei - Cordyceps sinensis - Grifola frondosa - Ganoderma lucidum - Coriolus versicolor - Lentinula edodes. The genoprotective potential of IA was evaluated for the first time. Significant antigenotoxic effects were detected in human peripheral blood cells against H2O2 induced DNA damage, in the pretreatment and in the posttreatment. The most efficient concentration of IA in pretreatment was 500 µg/mL, while in posttreatment it was the concentration of 250 µg/mL. Kinetics of attenuation of H2O2 induced DNA damage in posttreatment with the optimal concentration of IA showed significant decrease in the number of damaged cells at all time periods (15-60 min), reaching the greatest reduction after 15 and 45 min. Remarkable ·OH scavenging properties and moderate reducing power, together with the modest DPPH scavenging activity, could be responsible for the great attenuation of DNA damage after 15 min of exposure to IA, while reduction of DNA damage after 45 min could be the result in additional stimulation of the cell's repair machinery. Our results suggest that IA displayed antigenotoxic and antioxidant properties. A broader investigation of its profile in biological systems is needed.

Microwave synthesis of iodine-doped bismuth oxychloride microspheres for the visible light photocatalytic removal of toxic hydroxyl-contained intermediates of parabens: catalyst synthesis, characterization, and mechanism insight.

The iodine-doped bismuth oxychloride (I-doped BiOCl) microspheres are synthesized as the visible light photocatalysts for the photocatalytic removal of three toxic hydroxyl-contained intermediates of parabens. With the aid of the unique heating mode of microwave method, the I-doped BiOCl photocatalysts with tunable iodine contents and dispersed energy bands, instead of a mixture of BiOI and BiOCl or solid solution, are synthesized under the controllable conditions. Due to the stretched architectures, high specific surface area, and effective separation of photogenerated carriers, they exhibit high activity to the photocatalytic degradation of methyl 2,4-dihydroxybenzoate (MDB), methyl 3,4-dihydroxybenzoate (MDHB), and ethyl 2,4-dihydroxybenzoate (EDB). As a typical result, it is indicated that though MDB as the most difficult intermediate of parabens to be degraded, a 91.2% removal ratio can still be achieved over the I-doped BiOCl with an energy band of 2.79 eV within 60 min. In addition, it is also confirmed that these photocatalysts remain stable throughout the photocatalytic reaction and can be reused, and more importantly, the photogenerated h+ and •O2- are the key reactive species, while •OH plays a negligible role in the photocatalytic reaction. Resorcinol was identified as the main photodegraded intermediate. These results demonstrate that this photocatalytic system not only exhibit a high efficiency but also avoid the consequent secondary pollutions due to the no formation of complex hydroxyl derivatives.

Serum electrolytes can promote hydroxyl radical-initiated biomolecular damage from inflammation.

Chronic inflammatory disorders are associated with biomolecular damage attributed partly to reactions with Reactive Oxygen Species (ROS), particularly hydroxyl radicals (•OH). However, the impacts of serum electrolytes on ROS-associated damage has received little attention. We demonstrate that the conversion of •OH to carbonate and halogen radicals via reactions with serum-relevant carbonate and halide concentrations fundamentally alters the targeting of amino acids and loss of enzymatic activity in catalase, albumin and carbonic anhydrase, three important blood proteins. Chemical kinetic modeling indicated that carbonate and halogen radical concentrations should exceed •OH concentrations by 6 and 2 orders of magnitude, respectively. Steady-state γ-radiolysis experiments demonstrated that serum-level carbonates and halides increased tyrosine, tryptophan and enzymatic activity losses in catalase up to 6-fold. These outcomes were specific to carbonates and halides, not general ionic strength effects. Serum carbonates and halides increased the degradation of tyrosines and methionines in albumin, and increased the degradation of histidines while decreasing enzymatic activity loss in carbonic anhydrase. Serum electrolytes increased the degradation of tyrosines, tryptophans and enzymatic activity in the model enzyme, ketosteroid isomerase, predominantly due to carbonate radical reactions. Treatment of a mutant ketosteroid isomerase indicated that preferential targeting of the active site tyrosine accounted for half of the total tyrosine loss. The results suggest that carbonate and halogen radicals may be more significant than •OH as drivers for protein degradation in serum. Accounting for the selective targeting of biomolecules by these daughter radicals is important for developing a mechanistic understanding of the consequences of oxidative stress.

Nanocatalysts-Augmented and Photothermal-Enhanced Tumor-Specific Sequential Nanocatalytic Therapy in Both NIR-I and NIR-II Biowindows.

The tumor microenvironment (TME) has been increasingly recognized as a crucial contributor to tumorigenesis. Based on the unique TME for achieving tumor-specific therapy, here a novel concept of photothermal-enhanced sequential nanocatalytic therapy in both NIR-I and NIR-II biowindows is proposed, which innovatively changes the condition of nanocatalytic Fenton reaction for production of highly efficient hydroxyl radicals (•OH) and consequently suppressing the tumor growth. Evidence suggests that glucose plays a vital role in powering cancer progression. Encouraged by the oxidation of glucose to gluconic acid and H2 O2 by glucose oxidase (GOD), an Fe3 O4 /GOD-functionalized polypyrrole (PPy)-based composite nanocatalyst is constructed to achieve diagnostic imaging-guided, photothermal-enhanced, and TME-specific sequential nanocatalytic tumor therapy. The consumption of intratumoral glucose by GOD leads to the in situ elevation of the H2 O2 level, and the integrated Fe3 O4 component then catalyzes H2 O2 into highly toxic •OH to efficiently induce cancer-cell death. Importantly, the high photothermal-conversion efficiency (66.4% in NIR-II biowindow) of the PPy component elevates the local tumor temperature in both NIR-I and NIR-II biowindows to substaintially accelerate and improve the nanocatalytic disproportionation degree of H2 O2 for enhancing the nanocatalytic-therapeutic efficacy, which successfully achieves a remarkable synergistic anticancer outcome with minimal side effects.

Photocatalytic production of hydroxyl radicals by commercial TiO2 nanoparticles and phototoxic hazard identification.

This study identifies the phototoxic potential of commercial titanium dioxide nanoparticles (TiO2 NPs) used in sunscreens and consumer products by employing a tiered testing approach comprising physicochemical, in vitro and ex vivo tests. Our results revealed that all the test samples of TiO2 NPs, varied in surface coating, crystallinity and primary particle size, produced hydroxyl radicals upon UVA photoexcitation as determined by electron spin resonance (ESR) spectroscopy. Their phototoxic potentials were assessed first by combining the validated 3T3 neutral red uptake phototoxicity test and red blood cell phototoxicity test and subsequently in ex vivo models of chick chorioallantoic membrane (CAM) and reconstructed human 3D skin model (H3D). Crystalline structure and particle size of TiO2 NPs were found to exert a major influence on the photocatalytic activity and the associated phototoxic effects. Besides, a medium-sized sample with silica/alumina also exhibited high phototoxic potency with no obvious relevance to the enhanced hydroxyl radicals and lipidperoxidation. This effect might be taken place through the interaction of harmful metal ions released from the oxide coating. However, no phototoxicity was observed on a H3D skin model probably due to the lack of efficient percutaneous absorption of TiO2 NPs. This study demonstrates the efficacy of a tiered testing strategy for identifying phototoxic hazards of TiO2 NPs and suggests the need for a comprehensive assessment that takes account of the effects of different coating materials and potential interactions between multiple mechanisms.

Exposure of Microcystis aeruginosa to hydrogen peroxide and titanium dioxide under visible light conditions: Modeling the impact of hydrogen peroxide and hydroxyl radical on cell rupture and microcystin degradation.

The aims of this study are to evaluate, under visible light conditions, the ability of H2O2 and TiO2 to produce OH, their quantitative impacts on the cell integrity of Microcystis, and the subsequent release and degradation of microcystins (MCs). A sequential reaction model was developed, including one sub-model to simulate the rupture kinetics for cell integrity of Microcystis, and another to describe the release and degradation of MCs. For cell rupture, the dual-oxidant Delayed Chick-Watson model (DCWM) and dual-oxidant Hom model (HM) were first proposed and developed, giving excellent simulation results of cell rupture kinetics. Kinetic rate constants between Microcystis cells and H2O2 [Formula: see text] as well as OH (k•OH, Cell) under visible light successfully separated the individual effects of H2O2 and OH on Microcystis. The dual-oxidant models were further validated with additional experiments, making the models more convincing. Finally, the dual-oxidant cell rupture models were integrated with the MC degradation model and well predicted the observed MCs concentrations in the experimental systems. The results of this study not only demonstrate the potential application of H2O2 and TiO2 for the control of cyanobacteria and metabolites in natural water bodies, but also provide a new methodology to differentiate the individual contributions of the two oxidants, H2O2 and OH, on cell rupture, thus giving a novel way to more precisely determine the effective doses of applied oxidants for cyanobacteria control.

Induced sperm oxidative stress in dogs: Susceptibility against different reactive oxygen species and protective role of seminal plasma.

Oxidative stress (OS) is characterized by an unbalance between increased levels of reactive oxygen species (ROS) and/or impaired antioxidant protection. In this context, the composition of seminal plasma (SP) plays a key role in protecting sperm against OS. However, reproductive biotechnologies applied to dogs recommend the removal of SP. Thus, antioxidant therapy may be an important alternative when applying biotechniques such as semen cryopreservation in this specie. However, in order to be efficient, the choice of the ideal antioxidant in each condition is essential since each ROS is preferably neutralized by different antioxidant systems. Therefore, this study aims to evaluate the susceptibility of canine spermatozoa to different oxidative challenges (superoxide anion [O2-], hydrogen peroxide [H2O2], hydroxyl radical [OH-] and malondialdehyde [MDA]) in the present or absence of SP. We used ejaculates of eight dogs and submitted to induce oxidative challenges (with or without SP). After incubations, samples were evaluated for the susceptibility to lipid peroxidation, motility, mitochondrial activity and function, DNA integrity, plasma membrane and acrosome integrity. Sperm with SP had mitochondrial function preserved against ROS. However, in the absence of SP, H2O2 reduced mitochondrial membrane potential. In addition, regardless on SP, H2O2 was deleterious to sperm kinetics and plasma/acrosomal membranes. Incubation with OH- reduced mitochondrial activity and increased DNA fragmentation also independent on the absence of presence of SP. Furthermore, samples with SP were more resistant to lipid peroxidation (i.e., decreased concentration of TBARS). In conclusion, H2O2 and OH- appears to be the most deleterious ROS to dog sperm and SP protects the spermatozoa against mitochondrial injuries and lipid peroxidation.

Solar light irradiation significantly reduced cytotoxicity and disinfection byproducts in chlorinated reclaimed water.

Chlorinated reclaimed water is widely used for landscaping and recreational purposes, resulting in human exposure to toxic disinfection byproducts. Although the quality of chlorinated reclaimed water might be affected by sunlight during storage, the effects of solar light irradiation on the toxicity remain unknown. This study investigated the changes in cytotoxicity and total organic halogen (TOX) of chlorinated reclaimed water exposed to solar light. Irradiation with solar light for 12 h was found to significantly reduce the cytotoxicity of chlorinated reclaimed water by about 75%, with ultraviolet light being responsible for the majority of this reduction. Chlorine residual in reclaimed water tended to increase the cytotoxicity, and the synergy between solar light and free chlorine could not enhance the reduction of cytotoxicity. Adding hydroxyl radical scavengers revealed that the contribution of hydroxyl radical to cytotoxicity reduction was limited. Solar light irradiation concurrently reduced TOX. The low molecular weight (<1 kDa) fraction was the major contributor of cytotoxicity and TOX in chlorinated reclaimed water. Detoxification of the low molecular weight fraction by light irradiation was mainly a result of TOX dehalogenation, while detoxification of the high molecular weight (>1 kDa) fraction was probably caused by photoconversion from high toxic TOX to low toxic TOX.

Suplatast tosilate protects the lung against hyperoxic lung injury by scavenging hydroxyl radicals.

Prolonged exposure to hyperoxia produces extraordinary amounts of reactive oxygen species (ROS) in the lung and causes hyperoxic lung injury. Although supraphysiological oxygen is routinely administered for the management of respiratory failure, there is no effective strategy to prevent hyperoxic lung injury. In our previous study, we showed that suplatast tosilate, an asthma drug that inhibits T helper 2 (Th2) cytokines, ameliorated bleomycin-induced lung injury and fibrosis through Th2-independent mechanisms. Because bleomycin also generates ROS, we hypothesized that suplatast tosilate might have antioxidant activity and protect the lung against hyperoxic lung injury. To test this hypothesis, mice exposed to hyperoxia were given suplatast tosilate through drinking water. Treatment with suplatast tosilate significantly prolonged mouse survival, reduced the increases in the numbers of inflammatory cells, levels of the pro-inflammatory cytokines/chemokines IL-6 and MCP-1, and protein in bronchoalveolar lavage fluid, and ameliorated lung injury in histological assessment. Suplatast tosilate treatment also significantly inhibited hyperoxia-induced elevations in the levels of 8-hydroxydeoxyguanosine, a marker of oxidative DNA damage, in bronchoalveolar lavage fluid and 8-isoprostane, a marker of lipid peroxidation, in lung tissue. This finding suggests that suplatast tosilate exerts an antioxidant activity in vivo. In addition, we investigated whether suplatast tosilate has a scavenging effect on hydroxyl radical, the most reactive and harmful ROS, using electron paramagnetic resonance spin-trapping. Suplatast tosilate was shown to scavenge hydroxyl radicals in a dose-dependent manner, and its reaction rate constant with hydroxyl radical was calculated as 2.6×1011M-1S-1, which is faster than that of several well-established antioxidants, such as ascorbate, glutathione, and cysteine. These results suggest that suplatast tosilate protects the lung against hyperoxic lung injury by decreasing the degree of oxidative stress induced by ROS, particularly by scavenging hydroxyl radicals. Suplatast tosilate might become a potential therapeutic for hyperoxic lung injury.

Mechanism of synergistic DNA damage induced by the hydroquinone metabolite of brominated phenolic environmental pollutants and Cu(II): Formation of DNA-Cu complex and site-specific production of hydroxyl radicals.

2,6-Dibromohydroquinone (2,6-DBrHQ) has been identified as an reactive metabolite of many brominated phenolic environmental pollutants such as tetrabromobisphenol-A (TBBPA), bromoxynil and 2,4,6-tribromophenol, and was also found as one of disinfection byproducts in drinking water. In this study, we found that the combination of 2,6-DBrHQ and Cu(II) together could induce synergistic DNA damage as measured by double strand breakage in plasmid DNA and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) formation, while either of them alone has no effect. 2,6-DBrHQ/Cu(II)-induced DNA damage could be inhibited by the Cu(I)-specific chelating agent bathocuproine disulfonate and catalase, but not by superoxide dismutase, nor by the typical hydroxyl radical (•OH) scavengers such as DMSO and mannitol. Interestingly, we found that Cu(II)/Cu(I) could be combined with DNA to form DNA-Cu(II)/Cu(I) complex by complementary application of low temperature direct ESR, circular dichroism, cyclic voltammetry and oxygen consumption methods; and the highly reactive •OH were produced synergistically by DNA-bound-Cu(I) with H2O2 produced by the redox reactions between 2,6-DBrHQ and Cu(II), which then immediately attack DNA in a site-specific manner as demonstrated by both fluorescent method and by ESR spin-trapping studies. Further DNA sequencing investigations provided more direct evidence that 2,6-DBrHQ/Cu(II) caused preferential cleavage at guanine, thymine and cytosine residues. Based on these data, we proposed that the synergistic DNA damage induced by 2,6-DBrHQ/Cu(II) might be due to the synergistic and site-specific production of •OH near the binding site of copper and DNA. Our findings may have broad biological and environmental implications for future research on the carcinogenic polyhalogenated phenolic compounds.

Evaluation of antioxidant activity of phenolic fractions from the leaves and petals of dandelion in human plasma treated with H2O2 and H2O2/Fe.

Taraxacum officinale (dandelion) is a widespread perennial of the Asteraceae family. Dandelion is a rich source of different bioactive compounds, including phenolic compounds, terpenes, carbohydrates, proteins, fatty acids, vitamin and minerals. However, the content of phenolics in tested extracts by various authors was not always well described. Dandelion is also a commonly available food with a long history of human use and as such poses little risk of harm. In this study, we focused on four different phenolic fractions from leaves and petals of dandelion, which might be of great interest. The objective was to investigate the antioxidant properties of the phenolic fractions from dandelion leaves and petals in vitro. Effects of four different phenolic fractions from dandelion leaves and petals on the production of thiobarbituric acid reactive substances (TBARS, a marker of lipid peroxidation) in human plasma were studied in vitro. Their antioxidant properties against human plasma protein carbonylation and oxidation of protein thiols induced by a strong biological oxidant - hydrogen peroxide (H2O2) or H2O2/Fe (a donor of hydroxyl radicals) were also examined. The tested fractions of dandelion (0.5-50 µg/mL; the incubation time - 30 min) inhibited plasma lipid peroxidation induced by H2O2 or H2O2/Fe. However, their antioxidant properties were not concentration-dependent. All tested samples also inhibited plasma protein carbonylation and oxidation of thiol groups in plasma proteins stimulated by oxidants (H2O2 and OH∙). The obtained results suggest that four tested dandelion fractions, especially phenolic fractions from petals which are recognized as better than leaves source of flavonoids, may be a new and promising source of natural compounds with antioxidant activity beneficial for diseases-associated with oxidative stress, and with changes of hemostasis.

Effects of morphology and surface hydroxyl on the toxicity of BiOCl in human HaCaT cells.

Recently, bismuth oxychloride nanomaterials (BiOCls) are showing great promise in pollutant removal. Residues from these environmental remediations are potential hazardous materials. Unfortunately, human health risks of BiOCls are still unexplored widely. In the present study, we focused on the influence of physicochemical properties on the cytotoxicity of BiOCls toward a human skin derived cell line (HaCaT). Results showed that morphology and surface hydroxyl both had a profound effect on the toxicity of BiOCls. Microsphere-shaped BiOCl caused less toxicity than nanosheet-shaped BiOCl because of weaker particle-membrane interactions, while the presence of surface hydroxyl on microsphere-shaped BiOCl significantly raised the toxicity owing to the increased interaction with cell membrane. Both microsphere-shaped BiOCl with surface hydroxyl and nanosheet-shaped BiOCl caused significant cell membrane damage (PI uptake and LDH release), however, based on the different mechanism. The former may be a predominant "chemical" mechanism involved an oxidative stress paradigm, as manifested by elevated ROS and depleted GSH, while the latter is mainly due to a direct "physical" damage to cell membrane. Both "physical" and "chemical" response led to cell death. Furthermore, a set of experiments including MMP collapse, cell cycle arrest, and apoptosis/necrosis were conducted to propose a scenario for toxicological aspects of BiOCls. Data presented here would help to enable the rational design of BiOCls for either reducing their unintended consequences or increasing their application potentials.

A sensitive fluorescent sensor for the detection of endogenous hydroxyl radicals in living cells and bacteria and direct imaging with respect to its ecotoxicity in living zebra fish.

We have synthesized a novel fluorescent probe, , which shown a high potential for imaging of endogenous ˙OH in living cells and various types of bacteria. In addition, it is an excellent sensor for in vivo imaging of ˙OH generated following treatment with TiO2NPs in zebra fish.

Methyl-esterified 3-hydroxybutyrate oligomers protect bacteria from hydroxyl radicals.

Bacteria rely mainly on enzymes, glutathione and other low-molecular weight thiols to overcome oxidative stress. However, hydroxyl radicals are the most cytotoxic reactive oxygen species, and no known enzymatic system exists for their detoxification. We now show that methyl-esterified dimers and trimers of 3-hydroxybutyrate (ME-3HB), produced by bacteria capable of polyhydroxybutyrate biosynthesis, have 3-fold greater hydroxyl radical-scavenging activity than glutathione and 11-fold higher activity than vitamin C or the monomer 3-hydroxybutyric acid. We found that ME-3HB oligomers protect hypersensitive yeast deletion mutants lacking oxidative stress-response genes from hydroxyl radical stress. Our results show that phaC and phaZ, encoding polymerase and depolymerase, respectively, are activated and polyhydroxybutyrate reserves are degraded for production of ME-3HB oligomers in bacteria infecting plant cells and exposed to hydroxyl radical stress. We found that ME-3HB oligomer production is widespread, especially in bacteria adapted to stressful environments. We discuss how ME-3HB oligomers could provide opportunities for numerous applications in human health.

Controllable one-pot synthesis of a nest-like Bi2WO6/BiVO4 composite with enhanced photocatalytic antifouling performance under visible light irradiation.

In this study, a novel visible-light-sensitive Bi2WO6/BiVO4 composite photocatalyst was controllably synthesized through a facile one-pot hydrothermal method. The Bi2WO6/BiVO4 composite exhibited a perfect nest-like hierarchical microsphere structure, which was constructed by the self-assembly of nanoplates with the assistance of polyvinylpyrrolidone (PVP). The growth mechanism of the Bi2WO6/BiVO4 composite and the effect of its structure on its photocatalytic performance was investigated and proposed. Experimental results showed that the Bi2WO6/BiVO4 composites displayed enhanced photocatalytic antifouling activities under visible light irradiation compared to pure Bi2WO6 and BiVO4. Bi2WO6/BiVO4-1 exhibited the best photocatalytic antifouling performance, and almost all (99.99%) Pseudomonas aeruginosa (P. aeruginosa), Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) bacteria were killed within 30 min. Moreover, the Bi2WO6/BiVO4-1 composite exhibited excellent stability and reusability in the cycled experiments. The photocatalytic antifouling mechanism was proposed based on the active species trapping experiments, revealing that the photo-induced holes (h(+)) and hydroxyl radicals (˙OH) could attack the cell wall and cytoplasmic membrane directly and lead to the death of bacteria. The obviously enhanced photocatalytic activity of the Bi2WO6/BiVO4-1 composite could be mainly attributed to the formation of heterojunctions, accelerating the separation of photo-induced electrons and holes. Furthermore, the large BET surface area combined with the wide photoabsorption region further improved the photocatalytic performance of the Bi2WO6/BiVO4-1 composite. This study provides a new strategy to develop novel composite photocatalysts with enhanced photocatalytic performance for marine antifouling and water purification.

Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: Influence of alkyl-chain length.

As emerging organic contaminants (EOCs), the ubiquitous presence of preservative parabens in water causes a serious environmental concern. Hydroxyl radical ((•)OH) is a strong oxidant that can degrade EOCs through photochemistry in surface water environments as well as in advanced oxidation processes (AOPs). To better understand the degradation mechanisms, kinetics, and products toxicity of the preservative parabens in aquatic environments and AOPs, the (•)OH-initiated degradation reactions of the four parabens were investigated systematically using a computational approach. The four studied parabens with increase of alkyl-chain length were methylparaben (MPB), ethylparaben (EPB), propylparaben (PPB), and dibutylparaben (BPB). Results showed that the four parabens can be initially attacked by (•)OH through (•)OH-addition and H-abstraction routes. The (•)OH-addition route was more important for the degradation of shorter alkyl-chain parabens like MPB and EPB, while the H-abstraction route was predominant for the degradation of parabens with longer alkyl-chain for example PPB and BPB. In assessing the aquatic toxicity of parabens and their degradation products using the model calculations, the products of the (•)OH-addition route were found to be more toxic to green algae than original parabens. Although all degradation products were less toxic to daphnia and fish than corresponding parental parabens, they could be still harmful to these aquatic organisms. Furthermore, as alkyl-chain length increased, the ecotoxicity of parabens and their degradation products was found to be also increased.