Facet modulation promotes synergy between TiO2 nanomaterials and dissolved organic matter in photocatalytic generation of reactive oxygen species.

Reactive oxygen species-mediated conversion of organic matter into humus: A meta-analysis on mechanisms and environmental implications.

Naturally occurring reactive oxygen species (ROS) are widely involved in many environmental processes. Here we investigated the ROS generation associated with the interaction between complexed natural clay minerals (CMs) and dissolved organic matter (DOM). Our results showed that among the nine chemical-reduced CMs (CR-CMs), the light brown CR-CM (CR-CM 7) generated the highest ROS via oxygenation, relying on the reactive structural Fe(II) (Fe species that can transfer electrons to oxygen) instead of total structural Fe(II) as previously reported. Moreover, DOM affected the oxygenation of CR-CMs differently. The tight interaction between DOM and CR-CM 7 formed DOM-complexed Fe, while the weak interaction between DOM and the dark gold CR-CM (CR-CM 1) and the black CR-CM (CR-CM 5) exhibited decreased efficiencies. Mechanism studies revealed that ROS were generated through three pathways but all followed a similar one-electron transfer process in the presence of DOM. We further developed a three-layer geobattery model system and demonstrated that long electron transfer driven by CR-CMs/DOM could extend ROS generation to several centimetres across the oxic-anoxic interface, even without redox switching. These findings offer new insights into CMs-involved ROS generation and associated organic matter transformation in natural environments.

The normal microbial occupants of the mammalian intestine are crucial for maintaining gut homeostasis, yet the mechanisms by which intestinal cells perceive and respond to the microbiota are largely unknown. Intestinal epithelial contact with commensal bacteria and/or their products has been shown to activate noninflammatory signaling pathways, such as extracellular signal-related kinase (ERK), thus influencing homeostatic processes. We previously demonstrated that commensal bacteria stimulate ERK pathway activity via interaction with formyl peptide receptors (FPRs). In the current study, we expand on these findings and show that commensal bacteria initiate ERK signaling through rapid FPR-dependent reactive oxygen species (ROS) generation and subsequent modulation of MAP kinase phosphatase redox status. ROS generation induced by the commensal bacteria Lactobacillus rhamnosus GG and the FPR peptide ligand, N-formyl-Met-Leu-Phe, was abolished in the presence of selective inhibitors for G protein-coupled signaling and FPR ligand interaction. In addition, pretreatment of cells with inhibitors of ROS generation attenuated commensal bacteria-induced ERK signaling, indicating that ROS generation is required for ERK pathway activation. Bacterial colonization also led to oxidative inactivation of the redox-sensitive and ERK-specific phosphatase, DUSP3/VHR, and consequent stimulation of ERK pathway signaling. Together, these data demonstrate that commensal bacteria and their products activate ROS signaling in an FPR-dependent manner and define a mechanism by which cellular ROS influences the ERK pathway through a redox-sensitive regulatory circuit.

مصرف بی‌رویه و نادرست آفت‌کش‌ها سبب آلودگی محیط زیست شده است. به منظور کاهش تحرک این ترکیبات در خاک و آلودگی محیط زیست، لزوم کمی نمودن سرنوشت علف‌کش‌هایی با مصرف خاکی وجود دارد. در این تحقیق جذب ماده آلی محلول با غلظت‌های 0، 10، 20، 40، 80 و 160 میلی‌گرم کربن آلی در لیتر در دو خاک در شرایط آزمایشگاهی و در دمای ثابت مورد بررسی قرار گرفت. همچنین تأثیر pH و ماده آلی محلول با غلظت‌های مختلف (0، 10، 40 و 160 میلی‌گرم در لیتر) بر جذب علف‌کش متری‌بیوزین (با مقادیر 5/1، 2، 3، 4، 5 و 6 میلی‌گرم در کیلوگرم) مورد مطالعه قرار گرفت. نتایج نشان داد که ماده آلی محلول بر روی خاک‌ها جذب سطحی شده و هم‌دماهای آن‌ها با مدل فروندلیچ مطابقت داشت. جذب سطحی علف‌کش متری‌بیوزین در هر دو خاک 1 و 2 در حضور ماده آلی محلول کاهش نشان داد. به‌طوری که بیشترین مقدار جذب متری‌بیوزین در هر دو خاک 1 و 2 در تیمار بدون حضور ماده آلی محلول به ترتیب 19/38 و 71/29 میلی‌گرم در کیلوگرم و کمترین میزان در تیمار 160 میلی‌گرم ماده آلی محلول در لیتر به ترتیب 75/7 و 42/5 میلی‌گرم در کیلوگرم بدست آمد. جذب متری‌بیوزین در دامنه pH 5/5-4 در خاک 1 و 2، در تیمار عدم حضور ماده آلی محلول به ترتیب 54/8 و 23/6 درصد بیشتر از تیمار حضور ماده آلی محلول محاسبه گردید. به‌طور کلی افزایش غلظت ماده آلی محلول، سبب کاهش جذب متری‌بیورزین بر روی دو خاک گردید.

Interaction of Cu with dissolved organic matter (DOM) is an important physicochemical process affecting Cu mobility in soils. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge and sludge compost on the sorption of Cu on an acidic sandy loam and a calcareous clay loam. In the presence of DOM, Cu sorption capacity decreased markedly for both soils, especially for the calcareous soil. The Cu sorption isotherms could be well described by the Freundlich equation (r2 = 0.99), and the binding intensity parameter of soils in the presence of sludge DOM was lower than compost DOM. An increase in DOM concentration significantly reduced the sorption of Cu by both soils. Within the Cu and DOM concentration range studied, the decrease in Cu sorption caused by sludge DOM was consistently greater than that of compost DOM. This might be attributed to the greater amount of hydrophobic fraction of DOM in the compost. Moreover, the reduction of Cu sorption caused by DOM was more obvious in the soil with higher pH. In addition, the sorption of Cu increased with an increase in pH for both soils without the addition of DOM, while Cu sorption in the presence of DOM was unexpectedly decreased with an increase in pH at a pH >6.8. This implied that DOM produced by sludge or other C-enriched organic wastes heavily applied on calcareous soils might facilitate the leaching loss of Cu because of the formation of soluble DOM-metal complexes.

Hypoxia is known to stimulate reactive oxygen species (ROS) generation. Because reduced glutathione (GSH) is compartmentalized in cytosol and mitochondria, we examined the specific role of mitochondrial GSH (mGSH) in the survival of hepatocytes during hypoxia (5% O2). 5% O2 stimulated ROS in HepG2 cells and cultured rat hepatocytes. Mitochondrial complex I and II inhibitors prevented this effect, whereas inhibition of nitric oxide synthesis with Nomega-nitro-L-arginine methyl ester hydrochloride or the peroxynitrite scavenger uric acid did not. Depletion of GSH stores in both cytosol and mitochondria enhanced the susceptibility of HepG2 cells or primary rat hepatocytes to 5% O2 exposure. However, this sensitization was abrogated by preventing mitochondrial ROS generation by complex I and II inhibition. Moreover, selective mGSH depletion by (R,S)-3-hydroxy-4-pentenoate that spared cytosol GSH levels sensitized rat hepatocytes to hypoxia because of enhanced ROS generation. GSH restoration by GSH ethyl ester or by blocking mitochondrial electron flow at complex I and II rescued (R,S)-3-hydroxy-4-pentenoate-treated hepatocytes to hypoxia-induced cell death. Thus, mGSH controls the survival of hepatocytes during hypoxia through the regulation of mitochondrial generation of oxidative stress.

Aggregation of TiO2 and Ag nanoparticles in soil solution – Effects of primary nanoparticle size and dissolved organic matter characteristics

Diabetes mellitus and fine particulate matter from diesel exhaust (DEP) are both important contributors to the development of cardiovascular disease (CVD). Diabetes mellitus is a progressive disease with a high mortality rate in patients suffering from CVD, resulting in diabetic cardiomyopathy. Elevated DEP levels in the air are attributed to the development of various CVDs, presumably since fine DEP (<2.5 µm in diameter) can be inhaled and gain access to the circulatory system. However, mechanisms defining how DEP affects diabetic or control cardiomyocyte function remain poorly understood. The purpose of the present study was to evaluate cardiomyocyte function and reactive oxygen species (ROS) generation in isolated rat ventricular myocytes exposed overnight to fine DEP (0.1 µg/ml), and/or high glucose (HG, 25.5 mM). Our hypothesis was that DEP exposure exacerbates contractile dysfunction via ROS generation in cardiomyocytes exposed to HG. Ventricular myocytes were isolated from male adult Sprague-Dawley rats cultured overnight and sarcomeric contractile properties were evaluated, including: peak shortening normalized to baseline (PS), time-to-90% shortening (TPS90), time-to-90% relengthening (TR90) and maximal velocities of shortening/relengthening (±dL/dt), using an IonOptix field-stimulator system. ROS generation was determined using hydroethidine/ethidium confocal microscopy. We found that DEP exposure significantly increased TR90, decreased PS and ±dL/dt, and enhanced intracellular ROS generation in myocytes exposed to HG. Further studies indicated that co-culture with antioxidants (0.25 mM Tiron and 0.5 mM N-Acetyl-L-cysteine) completely restored contractile function in DEP, HG and HG+DEP-treated myocytes. ROS generation was blocked in HG-treated cells with mitochondrial inhibition, while ROS generation was blocked in DEP-treated cells with NADPH oxidase inhibition. Our results suggest that DEP exacerbates myocardial dysfunction in isolated cardiomyocytes exposed to HG-containing media, which is potentially mediated by various ROS generation pathways.

Distinctive response of ROS generation to multi-spectral irradiations during DOM photodegradation from eutrophic and oligotrophic lakes.

Dissolved organic matter (DOM) exists widely in natural water, which inevitably influences microplastic (MP) photoaging. Nevertheless, the impacts of DOM fractions with diverse molecular structures on MP photoaging remain to be elucidated. This study explored the photoaging mechanisms of polylactic acid (PLA)-MPs and polystyrene (PS)-MPs in the presence of DOM and its subfractions (hydrophobic acid (HPOA), hydrophobic neutral (HPON), and hydrophilic (HPI)). Across DOM fractions, HPI exhibited the highest electron accepting capacity (23 μmol e- (mg C)-1) due to its abundant tannin-like species (36.8%) with carboxylic groups, which facilitated more reactive oxygen species generation (particularly hydroxyl radical), leading to the strongest photoaging rate of two MPs by HPI. However, the sequences of bond cleavage during photoaging of each MPs were not clearly shifted as revealed by two-dimensional infrared correlation spectra. Inconspicuous effects on the extent of PS- and PLA-MPs photoaging were observed for HPOA and HPON, respectively. This was mainly ascribed to the occurrence of inhibitory mechanisms (e.g., light-shielding and quenching effect) counteracting the reactive oxygen species-promoting effects. The findings identified the HPI fraction of DOM for promoting PS- and PLA-MPs photoaging rate and first constructed a link among DOM molecular structures, redox properties, and effects on MP photoaging.

Catalase overexpression attenuates angiotensinogen expression and apoptosis in diabetic mice

Aggregation Turns BODIPY Fluorophores into Photosensitizers: Reversibly Switching Intersystem Crossing On and Off for Smart Photodynamic Therapy

The biotic ligand model (BLM) for the acute toxicity of cationic metals to aquatic organisms incorporates the toxicity-modifying effects of dissolved organic matter (DOM), but the default parameterization (i.e., assuming 10% of DOM is humic acid) does not differentiate DOM from different sources. We exposed a cladoceran (Ceriodaphnia dubia) to Ag in the presence of DOM from filtered YCT (standard yeast-Cerophyll(R)-trout chow food recommended by the U.S. Environmental Protection Agency [EPA] for cladocerans), from the Suwannee River (GA, USA; relatively little anthropogenic input), and from the Desjardins Canal in Hamilton (ON, Canada; receives treated municipal wastewater effluent). In all three treatments, the dissolved organic carbon (DOC) concentration was 2 mg/L (the concentration following addition of YCT slurry at the U.S. EPA-recommended volume ratio). The average 48-h median effects concentration (EC50) ratios for dissolved Ag in the presence and absence of DOM [i.e., (EC50 with DOM)/(EC50 without DOM)] were as follows: Suwannee River, 1.6; Desjardins Canal, 2.2; and YCT filtrate, 26.8. Therefore, YCT filtrate provided much more protection against Ag toxicity than that provided by DOM from the surface waters. The major spectral characteristic that differentiated YCT filtrate from the other two types of DOM was a strong tryptophan peak in the excitation- emission matrix for YCT. These results have important implications for interpreting Ag toxicity tests in which organisms are fed YCT, and they suggest BLM-calculated toxicity predictions might be improved by incorporating specific chemical constituents or surrogate indices of DOM. Another component of the protective effect against Ag toxicity, however, might be that the dissolved fraction of YCT served as an energy and/or nutrient source for C. dubia.

Effects of dissolved organic matter on the environmental behavior and toxicity of metal nanomaterials: A review

Phototransformation of biochar-derived dissolved organic matter and the effects on photodegradation of imidacloprid in aqueous solution under ultraviolet light