Selective Oxidation of Clopidogrel by Peroxymonosulfate (PMS) and Sodium Halide (NaX) System: An NMR Study

A selective transformation of clopidogrel hydrogen sulfate (CLP) by reactive halogen species (HOX) generated from peroxymonosulfate (PMS) and sodium halide (NaX) is described. Other sustainable oxidants as well as different solvents have also been investigated. As result of this study, for each sodium salt the reaction conditions were optimized, and four different degradation products were formed. Three products were halogenated at C-2 on the thiophene ring and have concomitant functional transformation, such as N-oxide in the piperidine group. A halogenated endo-iminium product was also observed. With this condition, a fast preparation of known endo-iminium clopidogrel impurity (new counterion) was reported as well. The progress of the reaction was monitored using nuclear magnetic resonance spectroscopy as an analytical tool and all the products were characterized by 1D-, 2D-NMR and HRMS.

Enhancement of Photo-bromination of Phenol by Anthraquinone-2-sulphonate and Benzophenone: Implication for Photo-production of Organic Brominated Compounds by Dissolved Organic Matter in Marine Environment

Organobromine compounds are of great ecological risks due to their high toxicity on organisms. Photochemical halogenation reaction may represent an important natural formation process of natural organobromine compounds in marine environment. Here we reported the enhanced formation of bromophenols from phenol by sunlit anthraquinone-2-sulphonate (AQ2S) and benzophenone (BP) in aqueous bromide solutions. Quinones and aromatic ketones are ubiquitous components of dissolved organic matter (DOM) in surface waters, and AQ2S and BP were adopted here as proxies of DOM. Bromophenols’ formation increased with the increasing of the concentrations of AQ2S and BP, and the promotion effect was in the order AQ2S > BP, indicating that sunlit DOM plays an important role for the formation of reactive bromine species. Chloride was found to promote the formation of bromophenols obviously, suggesting a possible role of the mixed reactive halogen species. Finally, the natural DOM from Suwannee River was found to enhance photobromoination at a low concentration (1 mg L-1) in aqueous bromide solution. Our results demonstrated the importance of reactive halogen species generation from sunlit DOM, which possibly contributes to the abiotic source of organohalogen compounds in marine environment.

DNA interstrand cross-links induced by the major oxidative adenine lesion 7,8-dihydro-8-oxoadenine

Oxidative damage to DNA generates 7,8-dihydro-8-oxoguanine (oxoG) and 7,8-dihydro-8-oxoadenine (oxoA) as two major lesions. Despite the comparable prevalence of these lesions, the biological effects of oxoA remain poorly characterized. Here we report the discovery of a class of DNA interstrand cross-links (ICLs) involving oxidized nucleobases. Under oxidative conditions, oxoA, but not oxoG, readily reacts with an opposite base to produce ICLs, highlighting a latent alkylating nature of oxoA. Reactive halogen species, one-electron oxidants, and the myeloperoxidase/H2O2/Cl− system induce oxoA ICLs, suggesting that oxoA-mediated cross-links may arise endogenously. Nucleobase analog studies suggest C2-oxoA is covalently linked to N2-guanine and N3-adenine for the oxoA-G and oxoA-A ICLs, respectively. The oxoA ICLs presumably form via the oxidative activation of oxoA followed by the nucleophilic attack by an opposite base. Our findings provide insights into oxoA-mediated mutagenesis and contribute towards investigations of oxidative stress-induced ICLs and oxoA-based latent alkylating agents.

Chemical interactions between ship-originated air pollutants and ocean-emitted halogens

<p>Ocean-going ships supply products from one region to another and contribute to the world’s economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of Reactive Halogen Species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated WRF-Chem model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO<sub>2</sub> at the surface, increase O<sub>3</sub> in the South China Sea, but decrease O<sub>3</sub> in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants and those of the oxidants with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate.</p>

Towards an advanced description and modelling of the atmospheric multiphase chemistry of mercury: CAPRAM HG module 1.0

<p>Mercury is a neurotoxic element emitted predominantly in its less-reactive form as gaseous elemental mercury (GEM) into the atmosphere by various natural and anthropogenic processes. Once emitted it undergoes chemical processing in the atmospheric gas and aqueous phase. There, GEM is oxidised into gaseous oxidised mercury (GOM), which partitions into aerosol particles residing there as particulate bounded mercury (PBM) due to its much higher solubility. The faster deposition of GOM and PBM compared to GEM is of special environmental importance, because they can be converted into more toxic organic mercury in aquatic environments and then take serious place in the food web. Thus, it is crucial for models to understand the transformation of GEM into GOM and PBM and vice versa. To date, numerous gas-phase chemistry simulations were performed, but reveal missing oxidation and reduction processes. However, only few models exist that investigate the multiphase mercury chemistry in a detailed manner.</p><p>Therefore, a comprehensive multiphase mercury chemistry mechanism, the CAPRAM HG module 1.0 (CAPRAM-HG1.0), has been developed. The CAPRAM-HG1.0 includes 74 gas-phase reactions, 22 phase transfers and 77 aqueous-phase reactions. It was coupled to the multiphase chemistry mechanism MCMv3.2/CAPRAM4.0 and the extended CAPRAM halogen module 3.0 (CAPRAM-HM3.0) for investigations of multiphase Hg redox under Chinese polluted conditions. Simulations were performed for summer conditions in 2014 using the air parcel model SPACCIM to investigate the performance of the model to simulate typical concentrations and patterns of GEM, GOM and PBM.</p><p>Under non-cloud conditions, model results reveal good coincides with concentrations and patterns for GEM, GOM and PBM measured in China. However, the simulations also show that there are still high uncertainties in atmospheric mercury chemistry. Especially, the complexation with HULIS within aerosol particles needs evaluation as the simulations indicate this process as key process driving concentrations and patterns of both GOM and PBM. Further, the present study demonstrates the need of a better understanding of continental concentrations of reactive halogen species and particle bounded halides as well as their link to the multiphase chemistry and atmospheric cycling of mercury.</p>

Is there an ozone depletion in volcanic plumes?

<p>Volcanic plumes are known to contain reactive halogen species, especially bromine oxide. Therefore, local ozone (O<sub>3</sub>) depletion (OD) is expected inside volcanic plumes. This OD has been measured in several field studies and is also found in several modelling studies. Recently, in order to quantify O<sub>3</sub> mixing ratios in volcanic plumes, mainly UV absorption monitors have been used as these have become the standard technique for ambient O<sub>3</sub> monitoring. However, these instruments show a large positive interference with sulphur dioxide (SO<sub>2</sub>). In fact, these instruments are approximately only 100 times more sensitive to O<sub>3</sub> than to SO<sub>2</sub>. This poses a significant problem for volcanic measurements since SO<sub>2 </sub>mixing ratios can exceed O<sub>3 </sub>mixing ratios by factors of 1000 or more. Thus, laborious SO<sub>2</sub> filtering introducing further problems, as e.g. humidity dependence, needed to be employed.</p><p>In this work simultaneous O<sub>3</sub> measurements inside a fumarole were conducted with a compact and mobile (backpack-size, ~10kg) chemiluminescence (CL) ozone monitor and a conventional UV absorption monitor at the summit of Mt Etna volcano, Italy. In parallel, SO<sub>2</sub> and CO<sub>2</sub> measurements were carried out with a MultiGAS-instrument. The CL monitor was used since no interference from trace gases contained in volcanic plumes is expected. Indeed, in this first field study inside a fumarole, we observed no significant interference with volcanic SO<sub>2 </sub>concentrations for the CL monitor. Under field conditions the CL monitor’s detection limit was determined to be ~1 ppb (1σ) at an integration time of 1 second.</p><p>Additionally, a rough calculation to estimate the expected OD in volcanic plumes was made. Contrary to popular belief, this calculation suggests for typical bromine oxide concentrations no significant (i.e. <1%) reactive halogen catalysed O<sub>3</sub>-loss in volcanic plumes.</p>

Humic Acid Extracts Leading to the Photochemical Bromination of Phenol in Aqueous Bromide Solutions: Influences of Aromatic Components, Polarity and Photochemical Activity

Dissolved organic matter (DOM) is considered to play an important role in the abiotic transformation of organobromine compounds in marine environment, for it produces reactive intermediates photochemically and is recognized as a significant source of reactive halogen species in seawater. However, due to the complex composition of DOM, the relationship between the natural properties of DOM and its ability to produce organobromine compounds is less understood. Here, humic acid (HA) was extracted and fractionated based on the polarity and hydrophobicity using silica gel, and the influences of different fractions (FA, FB and FC) on the photochemical bromination of phenol was investigated. The structural properties of HA fractions were characterized by UV-vis absorption, Fourier transform infrared spectroscopy and fluorescence spectroscopy, and the photochemical reactivity of HA fractions was assessed by probing triplet dissolved organic matter (3DOM*), singlet oxygen (1O2) and hydroxyl radical (•OH). The influences of HA fractions on the photo-bromination of phenol were investigated in aqueous bromide solutions under simulated solar light irradiation. FA and FB with more aromatic and polar contents enhanced the photo-bromination of phenol more than the weaker polar and aromatic FC. This could be attributed to the different composition and chemical properties of the three HAs’ fractions and their production ability of •OH and 3DOM*. Separating and investigating the components with different chemical properties in DOM is of great significance for the assessment of their environmental impacts on the geochemical cycle of organic halogen.

Nano-TiO2 Phototoxicity in Fresh and Seawater: Daphnia magna and Artemia sp. as Proxies

Nowadays, the industry is quite commonly using nanoparticles of titanium dioxide (nTiO2) especially in sunscreens, due to its higher reflective index in comparison to micron size TiO2. Its high demand causes its widespread environmental occurrence, thus damaging the environment. The aquatic ecosystems are the most vulnerable to contamination by nTiO2. Like other engineered nanoparticles, nTiO2 has demonstrated generation of reactive oxygen species (ROS) and reactive halogen species (RHS) in the aquatic environment under UV radiation. This study investigated the toxicity of nTiO2 towards two aquatic indicator organisms, one from freshwater (Daphnia magna) and the other from seawater (Artemia sp.), under simulated solar radiation (SSR). Daphnia magna and Artemia sp. were co-exposed in 16 h SSR and 8 h darkness cycles to different concentrations of nTiO2. The estimated EC50 at 48 h for D. magna was 3.16 mg nTiO2/L, whereas for A. sp. no toxic effects were observed. When we exposed these two organisms simultaneously to 48 h of prolonged SSR using higher nTiO2 concentrations, EC50 values of 7.60 mg/L and 5.59 mg/L nTiO2 for D. magna and A. sp., respectively, were obtained. A complementary bioassay was carried out with A. sp., by exposing this organism to a mixture of nTiO2 and organic UV filters (benzophenone 3 (oxybenzone, BP3), octocrylene (OC), and ethyl 4-aminobenzoate (EtPABA)), and then exposed to SSR. The results suggested that nTiO2 could potentially have negative impacts on these organisms, also this work outlines the different characteristics and interactions that may contribute to the mechanisms of environmental (in salted and freshwater) phototoxicity of nTiO2 and UV radiation, besides their interaction with organic compounds.