Peroxide stabilizers remarkably increase the longevity of thermally activated peroxydisulfate for enhanced ISCO remediation.

Thermally activated peroxydisulfate In Situ Chemical Oxidation (TAP-ISCO) is often applied for the remediation of soil-sorbed hydrophobic organic contaminants (HOCs) and nonaqueous phase liquids (NAPLs), which act as long-term sources of groundwater contamination. TAP-ISCO benefits from improved desorption/dissolution of organic contaminants into the aqueous phase and efficient activation of peroxydisulfate at elevated temperatures, but the primary limitation of TAP-ISCO is the short lifetime of peroxydisulfate (therefore the availability of reactive radical species). To resolve this problem, coupling of peroxide stabilizers with TAP were tested. The compatibility of seven representative commercial organic and inorganic peroxide stabilizers, including sodium stannate, trisodium phosphate, sodium pyrophosphate, sodium silicate, sodium citrate, ethylene diamine tetra methylene phosphonic acid and ethylenediaminetetraacetic acid disodium salt, with TAP in aqueous solutions and solutions containing goethite or soil particles were first studied. The effects of stabilizers on the formation, distribution and reactivity of reactive oxygen species were then investigated through electron paramagnetic resonance (EPR) spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide, chemical probe experiments using anisole, nitrobenzene and hexachloroethane, and biphasic trichloroethylene (TCE) dense nonaqueous phase liquids (DNAPLs) TAP-ISCO mimicking experiments. The results indicate that organic stabilizers significantly accelerate peroxydisulfate decomposition at both ambient and elevated temperatures. In contrast, inorganic stabilizers can markedly increase peroxydisulfate longevity by suppressing the acid-catalyzed peroxydisulfate decomposition, quenching radical-chain acceleration, and sequestering transition metal species. In addition, TAP systems containing inorganic stabilizers can effectively generate a variety of reactive radical species, including SO4•-, HO•, and O2•-, and improve the oxidation of anisole and nitrobenzene, though suppressing the reduction of hexachloroethane to some extent. Especially, suitable inorganic stabilizers (e.g., trisodium phosphate) can effectively improve TAP oxidation of TCE DNAPL while suppressing peroxydisulfate decomposition. Overall, this study provides the fundamental basis of coupling TAP-ISCO with peroxide stabilizers.

Twofold and Threefold Sinusoidal Patterns in Coupled Molecular Motions of 184,025 Structures of Phenylethane, Nitroethane, and Carboxylate Derivatives.

Scatter plot analyses for 14,169 phenylethanes of the substructure Cß-CαH2-Ph with three open coordination positions at Cß and 150,568 phenylethanes of Cß-CαHX-Ph with an additional open coordination position X at Cα have been performed, based on searches in the Cambridge Structural Database. The correlation of rotation angle ψ = Cß-Cα-Ci-Co with a pyramidalization angle θ = Co-Co'-Ci-Cα in a 360° rotation about the bond Cα-Ci reveals a sinusoidal pattern with three maxima and minima, whereas the correlation of rotation angle ψ with bond angle ω = Cß-Cα-Ci and bond length d = Cß-Cα results in sinusoidal patterns with two maxima and minima. A total of 3993 nitro derivatives of the substructure Cß-CαHX-NO2 confirm the results and show that atoms Ci/Co/Co' in the phenyl compounds can be replaced by atoms N/O/O' without any change in the two- and threefold patterns. In 15,295 methyl acetates of the substructure Cß-CαHX-C'(═O)OMe, pyramidalization of the group CαC'(═O)OMe results in a chiral flat tetrahedron with four different corners. (Rθ)/(Sθ) selectivity in the configuration of the tetrahedron is induced by the bonds Cα-Cß, Cα-H, and Cα-X, emanating from the tetrahedral center Cα. It is surprising that bonds as different as Cα-Cß, Cα-H, and Cα-X (X = H, C, N, O, S, etc.) give almost the same induction intensities.

Resolving Bromonitromethane Sourcing by Synthesis: Preparation at the Decagram Scale.

The accessibility of bromonitromethane has declined in recent years, limiting its viability as a reagent for chemical synthesis. The reinvestigation and optimization of a variety of preparations, and the development of safe operating principles, are described. The reproducible protocol described here leverages the effectiveness of hydroxide for nitromethane bromination while respecting its incompatibility with the product it forms. This careful balance was achieved at scales up to 56 g, resulting in a reproducible procedure that provides straightforward, sustainable, and affordable access to this critical reagent.

Discovery of novel purinylthiazolylethanone derivatives as anti-Candida albicans agents through possible multifaceted mechanisms.

An unprecedented amount of fungal and fungal-like infections has recently brought about some of the most severe die-offs and extinctions due to fungal drug resistance. Aimed to alleviate the situation, new effort was made to develop novel purinylthiazolylethanone derivatives, which were expected to combat the fungal drug resistance. Some prepared purinylthiazolylethanone derivatives possessed satisfactory inhibitory action towards the tested fungi, among which compound 8c gave a MIC value of 1 µg/mL against C. albicans. The active molecule 8c was able to kill C. albicans with undetectable resistance as well as low hematotoxicity and cytotoxicity. Furthermore, it could hinder the growth of C. albicans biofilm, thus avoiding the occurrence of drug resistance. Mechanism research manifested that purinylthiazolylethanone derivative 8c led to damage of cell wall and membrane disruption, so protein leakage and the cytoplasmic membrane depolarization were observed. On this account, the activity of fungal lactate dehydrogenase was reduced and metabolism was impeded. Meanwhile, the increased levels of reactive oxygen species (ROS) and reactive nitrogen species (RNS) disordered redox equilibrium, giving rise to oxidative damage to fungal cells and fungicidal effect.

Hazard characterization of carcinogenicity, mutagenicity, and reproductive toxicity for short chain primary nitroalkanes.

Nitroalkanes are organic aliphatic hydrocarbon compounds with a nitro moiety that are commonly used as solvents or intermediates to synthesize a variety of organic compounds due to their inherent reactivity. In June 2020, a harmonized classification and labeling (CLH) proposal was submitted to the European Chemicals Agency (ECHA) for the following harmonized carcinogenicity, mutagenicity, and reproductive toxicity ("CMR") classifications for nitromethane (NM), nitroethane (NE), and 1-nitropropane (1-NP): NM Carc. 1B and Repr. 1B; NE Repr. 1B; and 1-NP Repr. 2. In this assessment, a weight of evidence (WoE) evaluation of studies on animal carcinogenicity and reproductive and developmental toxicity, genotoxicity, and mode of action for these three nitroalkanes was performed to critically assess the relevance of the proposed CMR classifications. Overall, the WoE indicates that NM, NE, and 1-NP are not carcinogenic, genotoxic, nor selective reproductive or developmental toxicants. Based on our analysis, classifying NM, NE, and 1-NP as Category 2 reproductive toxicants is most appropriate. Furthermore, not classifying NE and 1-NP with respect to their carcinogenicity is appropriate based on the available studies for this endpoint coupled with negative results in genotoxicity studies, metabolism data, and in silico predictions. We determined that the classification for NM of Carc. 1B is not appropriate, based on the fact that rat mammary and harderian tumors are likely not relevant to humans and lung and liver tumors reported in mice were equivocal in their dose-response and statistical significance.

Hexachloroethane dechlorination in sulfide-containing aqueous solutions catalyzed by nitrogen-doped carbon materials.

This study demonstrated that nitrogen-doped carbon materials (NCMs) could effectively catalyze the chlorine elimination process in hexachloroethane (HCA) declorination in sulfide-containing environments for the first time. The kobs values of HCA dechlorination by sulfide in the presence of 10 mg/L NCMs were higher than that of no mediator at pH 7.3 by one or two orders of magnitude. The catalytic capabilities of NCMs on HCA dechlorination were evident in common ranges of natural pH (5.3-8.9) and it could be accelerated by the increase of pH but be suppressed by the presence of dissolved humic acid. Moreover, NCMs exhibited much better catalytic capability on HCA dechlorination compared to the carbon materials, mainly owing to the combined contributions of pyridine N, including enhanced nucleophilic attack to HCA molecule by generating newborn C-S-S and activation of HCA molecule by elongating C-Cl bonds. The functions of pyridine N in micron-sized NCMs with mesopores were better than in nano-sized NCMs on HCA dechlorination. These findings displayed the potential of NCMs, when released into sulfide-containing environments, may significantly increase the dechlorination of chlorinated aliphatic hydrocarbons.

Acetylene-Fueled Trichloroethene Reductive Dechlorination in a Groundwater Enrichment Culture.

In aquifers, acetylene (C2H2) is a product of abiotic degradation of trichloroethene (TCE) catalyzed by in situ minerals. C2H2 can, in turn, inhibit multiple microbial processes including TCE dechlorination and metabolisms that commonly support dechlorination, in addition to supporting the growth of acetylenotrophic microorganisms. Previously, C2H2 was shown to support TCE reductive dechlorination in synthetic, laboratory-constructed cocultures containing the acetylenotroph Pelobacter sp. strain SFB93 and Dehalococcoides mccartyi strain 195 or strain BAV1. In this study, we demonstrate TCE and perchloroethene (PCE) reductive dechlorination by a microbial community enriched from contaminated groundwater and amended with C2H2 as the sole electron donor and organic carbon source. The metagenome of the stable, enriched community was analyzed to elucidate putative community functions. A novel anaerobic acetylenotroph in the phylum Actinobacteria was identified using metagenomic analysis. These results demonstrate that the coupling of acetylenotrophy and reductive dechlorination can occur in the environment with native bacteria and broaden our understanding of biotransformation at contaminated sites containing both TCE and C2H2IMPORTANCE Understanding the complex metabolisms of microbial communities in contaminated groundwaters is a challenge. PCE and TCE are among the most common groundwater contaminants in the United States that, when exposed to certain minerals, exhibit a unique abiotic degradation pathway in which C2H2 is a product. C2H2 can act as both an inhibitor of TCE dechlorination and of supporting metabolisms and an energy source for acetylenotrophic bacteria. Here, we combine laboratory microcosm studies with computational approaches to enrich and characterize an environmental microbial community that couples two uncommon metabolisms, demonstrating unique metabolic interactions only yet reported in synthetic, laboratory-constructed settings. Using this comprehensive approach, we have identified the first reported anaerobic acetylenotroph in the phylum Actinobacteria, demonstrating the yet-undescribed diversity of this metabolism that is widely considered to be uncommon.

Surface quinone-induced formation of aqueous reactive sulfur species controls pine wood biochar-mediated reductive dechlorination of hexachloroethane by sulfide.

Understanding the mechanisms controlling the redox transformation of organic contaminants mediated by biochar is of great significance for application of biochar in remediation of contaminated soils and sediments. Here we investigated the mediation effect of a pine wood-derived biochar (P-char) in comparison with multiwalled carbon nanotubes (MCNTs) and graphite on the reductive dechlorination of hexachloroethane by sulfide. Upon normalization of the mediator's surface area, the reduction rate of hexachloroethane follows an order of P-char < MCNTs < graphite. Aqueous polysulfides and polysulfide free radicals were readily produced by reacting sulfide only with P-char, and the supernatant separated from the reaction system could account for 83.4% of the pseudo-kinetic rate constant of hexachloroethane mediated by P-char. In contrast, MCNTs and graphite had weak abilities to produce reactive sulfur species, and the supernatant exhibited very low reduction capability (<20.7%) of hexachloroethane. Electron paramagnetic resonance (EPR) analysis demonstrated that the surface quinone moieties on P-char induced the formation of polysulfides and polysulfide free radicals from sulfide by serving as one-electron acceptors. Consistently, polysulfides prepared by reacting elemental sulfur with sulfide showed much stronger reducing capability compared to sulfide. Thus, the mediation effect of P-char was dominantly attributed to the surface quinone-induced formation of reactive reducing sulfur species, whereas the mediation effect of MCNTs and graphite mainly stemmed from the enhanced electron transfer by the graphitized carbon. These results showed for the first time that surface quinone-induced formation of aqueous reactive sulfur species could control biochar-mediated reductive dechlorination of chloroorganic contaminants by sulfides.

Multi-elemental C-Br-Cl isotope analysis for characterizing biotic and abiotic transformations of 1-bromo-2-chloroethane (BCE).

Multi-elemental C-Br-Cl compound-specific isotope analysis was applied for characterizing abiotic and biotic degradation of the environmental pollutant 1-bromo-2-chloroethane (BCE). Isotope effects were determined in the model processes following hydrolytic dehalogenation and dihaloelimination pathways as well as in a microcosm experiment by the microbial culture from the contaminated site. Hydrolytic dehalogenation of BCE under alkaline conditions and by DhaA enzyme resulted in similar dual isotope slopes (ɅC/Br 21.9 ± 4.7 and 19.4 ± 1.8, respectively, and ɅC/Cl ~ ∞). BCE transformation by cyanocobalamin (B12) and by Sulfurospirillum multivorans followed dihaloelimination and was accompanied by identical, within the uncertainty range, dual isotope slopes (ɅC/Br 8.4 ± 1.7 and 7.9 ± 4.2, respectively, and ɅC/Cl 2.4 ± 0.3 and 1.5 ± 0.6, respectively). Changes over time in the isotope composition of BCE from the contaminated groundwater showed only a slight variation in δ13C values and were not sufficient for the elucidation of the BCE degradation pathway in situ. However, an anaerobic microcosm experiment with the enrichment cultures from the contaminated groundwater presented dual isotope slopes similar to the hydrolytic pathway, suggesting that the potential for BCE degradation in situ by the hydrolytic dehalogenation pathway exists in the contaminated site.

Competitive aptasensor with gold nanoparticle dimers and magnetite nanoparticles for SERS-based determination of thrombin.

It is known that the intensity of surface-enhanced Raman scattering (SERS) of monomeric gold nanoparticles (GNPs) is insufficient for ultrasensitive analysis. The authors describe dimeric GNPs for use in a competitive SERS and aptamer based assay for thrombin. The reagent 1,2-bis(4-pyridyl) ethylene serves as both the coupling agent and the Raman reporter on the GNP dimers. In the presence of thrombin, the hybridization of two aptamers, one attached to the GNP dimers, the other to magnetic nanoparticles, is competitively prevented. This method takes advantage of the unique "hot spots" of the GNP dimers to amplify the Raman signal. This results in an ultra-sensitive thrombin assay when compared to assays using GNP monomers. The limit of detection is as low as 1 fM of thrombin. The Raman intensity, best measured at 1612 cm-1, increases linearly in the 1 fM to 10 nM thrombin concentration range. The method was applied to the determinaiton of thrombin in spiked simulated body fluid and human serum. Graphical abstract This method takes advantage of the unique "hot spots" of the gold nanoparticle dimers to amplify the Raman signal. The dimers are linked to the magnetic nanoparticles via an aptamer. The use of both competitive displacement and magnetic separation greatly improves the sensitivity of the thrombin assay.

Comparison of the health risks associated with different exposure pathways of multiple volatile chlorinated hydrocarbons in contaminated drinking groundwater.

A total of 152 groundwater samples were collected around a contaminated site to evaluate the carcinogenic and noncarcinogenic risks of exposure to twelve volatile chlorinated hydrocarbons (VCHs) by oral ingestion, dermal contact and inhalation absorption during showering. Although toxicity data of some VCHs are fragmentary, the results showed that the carcinogenic and noncarcinogenic risks of exposure to VCHs in contaminated drinking groundwater for local residents needs immediate attention. The main risk contributors for the carcinogenic and noncarcinogenic risks are carbon tetrachloride and 1,1,2-trichloroethane through inhalation exposure pathway, respectively. The health risk contribution rates associated with three exposure pathways for a specific VCH were intrinsic to the compound, and the dermal contact corresponded to a negligible contribution for almost every VCH species. Although most of the evaluated VCHs had a higher risk contribution by inhalation than by oral ingestion pathway, the integrated multi-VCH health risk contributions of the three exposure pathways were mainly dependent on the VCH compositions. Drinking boiled water not only decreased the exposure risk but also affected the risk contribution rates of three exposure pathways, which indicates that it is feasible to reduce the risk of VCH exposure during daily activities based on the risk contribution of the exposure pathways. In addition to the VCHs included in the drinking water standards, species such as 1,1,2,2-tetrachloroethane and hexachloroethane also showed a remarkable exposure health risk according to the standardized health risk calculation, which implied that improved drinking water standards are urgently required.

Enhanced hydrolysis of 1,1,2,2-tetrachloroethane by multi-walled carbon nanotube/TiO2 nanocomposites: The synergistic effect.

Once released into the environment, engineered nanomaterials can significantly influence the transformation and fate of organic contaminants. To date, the abilities of composite nanomaterials to catalyze environmentally relevant abiotic transformation reactions of organic contaminants are largely unknown. Herein, we investigated the effects of two nanocomposites - consisting of anatase titanium dioxide (TiO2) with different predominantly exposed crystal facets (i.e., {101} or {001} facets) anchored to hydroxylated multi-walled carbon nanotubes (OH-MWCNT) - on the hydrolysis of 1,1,2,2-tetrachloroethane (TeCA), a common groundwater contaminant, at ambient pH (6, 7 and 8). Both OH-MWCNT/TiO2 nanocomposites were more effective in catalyzing the dehydrochlorination of TeCA than the respective component materials (i.e., bare OH-MWCNT and bare TiO2). Moreover, the synergistic effect of the two components was evident, in that the incorporation of OH-MWCNT increased the TeCA adsorption capacity of the nanocomposites, significantly enhancing the catalytic effect of the deprotonated hydroxyl and carboxyl groups on nanocomposite surfaces, which served as the main catalytic sites for TeCA hydrolysis. The findings may have important implications for the understanding of the environmental implications of composite nanomaterials and may shed light on the design of high-performance nanocomposites for enhanced contaminant removal.

Structural Transformations in the Thermal Dehydration of [Cu2(bpa)(btec)(H2O)4]n Coordination Polymer.

Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In this context, the use of 1,2,4,5-benzenetetracarboxylic acid (H4btec) gave us a novel 2D compound, [Cu2(bpa)(btec)(H2O)4]n (1), which was prepared by microwave-assisted synthesis and structurally characterized by means of single crystal X-ray diffraction. Its thermal behavior was analyzed through thermogravimetric analysis and variable temperature powder X-ray diffraction, concluding that thermal stability is influenced by the coordination water molecules, allowing two sequential thermochromic phase transformations to take place. These transformations were monitored by electronic paramagnetic resonance spectroscopy and magnetic susceptibility measurements. In addition, the crystal structure of the anhydrous compound [Cu2(bpa)(btec)]n (1.ah) was determined. Finally, a topological study was carried out for the bpa ligand considering all the structures deposited in the Cambridge Structural Databased. More than 1000 structures were analyzed and classified into 17 different topologies, according to the role of the ligand.

Elucidating the dechlorination mechanism of hexachloroethane by Pd-doped zerovalent iron microparticles in dissolved lactic acid polymers using chromatography and indirect monitoring of iron corrosion.

The degradation mechanism of the pollutant hexachloroethane (HCA) by a suspension of Pd-doped zerovalent iron microparticles (Pd-mZVI) in dissolved lactic acid polymers and oligomers (referred to as PLA) was investigated using gas chromatography and the indirect monitoring of iron corrosion by continuous measurements of pH, oxidation-reduction potential (ORP), and conductivity. The first experiments took place in the absence of HCA, to understand the evolution of the Pd-mZVI/PLA/H2O system. This showed that the evolution of pH, ORP, and conductivity is related to changes in solution chemistry due to iron corrosion and that the system is initially cathodically controlled by H+ mass transport to Pd surfaces because of the presence of an extensive PLA layer. We then investigated the effects of Pd-mZVI particles, temperature, initial HCA concentration, and PLA content on the Pd-mZVI/PLA/HCA/H2O system, to obtain a better understanding of the degradation mechanism. In all cases, HCA dechlorination first requires the production of atomic hydrogen H*-involving the accumulation of tetrachloroethylene (PCE) as an intermediate-before its subsequent reduction to non-chlorinated C2 and C4 compounds. The ratio between Pd-mZVI dosage, initial HCA concentration, and PLA content affects the rate of H* generation as well as the rate-determining step of the process. A pseudo-first-order equation can be applied when Pd-mZVI dosage is much higher than the theoretical stoichiometry (600 mg for [HCA]0 = 5-20 mg L-1). Our results indicate that the HCA degradation mechanism includes mass transfer, sorption, surface reaction with H*, and desorption of the product.

Simultaneous analysis of haloacetonitriles, haloacetamides and halonitromethanes in chlorinated waters by gas chromatography-mass spectrometry.

Nitrogenous classes of disinfection by-products (DBPs), such as haloacetamides (HAAms), haloacetonitriles (HANs) and halonitromethanes (HNMs), while generally present at lower concentrations in disinfected waters than carbonaceous DBPs, such as trihalomethanes or haloacetic acids, have been shown to be more detrimental to human health. While several methods have been shown to be suitable for the analysis of some nitrogenous DBPs (N-DBPs) in disinfected waters, many are unable to quantify HAAms, the most detrimental to health of these three N-DBP classes. Here, we report the first method for the simultaneous analysis of twenty-five N-DBPs (nine HANs, nine HNMs and seven HAAms) in disinfected waters using liquid-liquid extraction followed by gas chromatography-mass spectrometry. The use of a programmable temperature vaporiser injector minimises degradation of the thermally labile HNMs, while avoiding the concomitant decreases in HANs and HAAms which occur when using lower injector temperatures. Extraction parameters, including sample pH, solvent volume, salt addition and sample pre-concentration, were investigated to determine the optimal conditions across all target N-DBPs. Good detection limits were achieved for all analytes (0.8-1.7 µg L-1) and both laboratory and instrumental runtimes were significantly reduced compared to previous methods. The method was validated for the analysis of N-DBPs in drinking, swimming pool and spa waters, and concentrations of up to 41 µg L-1 of some N-DBPs were measured in some pools.

Rapid and complete dehalogenation of halonitromethanes in simulated gastrointestinal tract and its influence on toxicity.

Halonitromethanes (HNMs) as one typical class of nitrogenous disinfection byproducts in drinking water and wastewater are receiving attentions due to their high toxicity. This study applied a simulator of the human gastrointestinal tract to determine the dehalogenation processes of trichloronitromethane, bromonitromethane and bromochloronitromethane for the first time. Influence of digestion process of HNMs on gut microbiota and hepatotoxicity was further analyzed. Results showed that the three HNMs were rapidly and completely dehalogenated in the gastrointestinal tract, especially in the stomach (2 h retention Time) and small intestine (4 h retention Time). Mucin, cysteine, pancreatin and bile salts in the digestive juice played major roles in the dehalogenation process. HNMs and their dehalogenation products in the resulting fluids of stomach induced the highest toxicity followed by those in intestine and colon, exhibiting dose-dependent effects. Although most HNMs were degraded in the stomach and small intestine, residual HNMs entered into colon changed the microbial community. Abundance of several genera, such as Bacteroides, Lachnospiraceae_unassigned and Lactobacillus had high correlation with exposure concentration of HNMs. This study sheds new light on dehalogenation and toxic processes of HNMs by oral exposure, which provides basic data for their human health risk assessment.

Reductive Hexachloroethane Degradation by S2O8•- with Thermal Activation of Persulfate under Anaerobic Conditions.

Despite that persulfate radical (S2O8•-) is an important radical species formed from the persulfate (PS) activation process, its reactivity toward contaminant degradation has rarely been explored. In this study, we found that S2O8•- efficiently degrades the contaminant hexachloroethane (HCA) under anaerobic conditions, whereas HCA degradation is negligible in the presence of oxygen. We observed dechlorination products such as pentachloroethane, tetrachloroethylene, and Cl- during HCA degradation, which suggest that HCA degradation is mainly a reductive process under anaerobic conditions. Using free radical quenching and electron paramagnetic resonance (EPR) experiments, we confirmed that S2O8•- forms from the reaction between sulfate radical (SO4•-) and S2O82-, which are the dominant reactive species in HCA degradation. Density functional theory (DFT) calculations were used to elucidate the pathways of HCA degradation and S2O8•- radical decomposition. Further investigation showed that S2O8•- can efficiently degrade HCA and DDTs in soil via reduction during the thermal activation of PS under anaerobic conditions. The finding of this study provide a novel strategy for the reductive degradation of contaminant when PS-based in situ chemical oxidation used in the remediation of soil and groundwater, particularly those contaminated with highly halogenated compounds.

Pre-treatment of anodic inoculum with nitroethane to improve performance of a microbial fuel cell.

Methanogenic substrate loss is reported to be a major bottleneck in microbial fuel cell (MFC), which significantly reduces the power production capacity and coulombic efficiency (CE) of this system. Nitroethane is found to be a potent inhibitor of hydrogenotrophic methanogens in rumen fermentation process. Influence of nitroethane pre-treated sewage sludge inoculum on suppressing the methanogenic activity and enhancing the electrogenesis in MFC was evaluated. MFC inoculated with nitroethane pre-treated anodic inoculum demonstrated a maximum operating voltage of 541 mV, with CE and maximum volumetric power density of 39.85% and 20.5 W/m3, respectively. Linear sweep voltammetry indicated a higher electron discharge on the anode surface due to enhancement of electrogenic activity while suppressing methanogenic activity. A 63% reduction in specific methanogenic activity was observed in anaerobic sludge pre-treated with nitroethane, emphasizing the significance of this pre-treatment for suppressing methanogenesis and its utility for enhancing electricity generation in MFC.

1,2-Diphenoxiethane salts as potent antiplasmodial agents.

In this article we present a series of non-cytotoxic potent human choline kinase (CK) inhibitors that exhibit nanomolar antiplasmodial activity in vitro. The most active antiplasmodial compounds, 10a-b, bearing a pyridinium cationic head were inactive against CK, while compounds 10g and 10j with a quinolinium moiety exhibit moderate inhibition of both the parasite and the enzyme. The results point towards an additional mechanism of action unrelated to CK inhibition that remains to be established.

Crystal structure of hypothetical protein PA4202 from Pseudomonas aeruginosa PAO1 in complex with nitroethane as a nitroalkane substrate.

Nitroalkane oxidase (NAO) and nitronate monooxygenase (NMO) are two different types of nitroalkane oxidizing flavoenzymes identified in nature. A previous study suggested that the hypothetical protein PA4202 from Pseudomonas aeruginosa PAO1 is NMO and utilizes only anionic nitronates. However, the structural similarity between the PA4202 protein and Streptomyces ansochromogenes NAO has motivated investigation for what features of the two enzymes differentiate between the NAO and NMO activities. Herein, we report the crystal structure of PA4202 in a ternary complex with a neutral nitroethane (NE) and flavin mononucleotide (FMN) cofactor to elucidate the substrate recognition mechanism using a site-directed mutagenesis. The ternary complex structure indicates that the NE is bound with an orientation, which is poised for the proton transfer to H183 (which is the essential first catalytic step with nitroalkanes), and subsequent reactions with FMN. Moreover, a kinetic study reveals that the catalytic reactions of the wild type and H183 mutants PA4202s with nitroalkane substrates may yield the products of hydrogen peroxide and nitrite that are specified to NAO, although they show a low catalytic efficiency. Our results provide the first structure-based molecular insight into the substrate binding property of the hypothetical protein PA4202, including the interactions with neutral nitroalkanes as the substrate.