Degradation kinetics and mechanism of bis(2-chloroethyl) ether by electromagnetic induction electrodeless lamp activated persulfate.

Bis(2-chloroethyl) ether (BCEE) has become one of the most frequently detected chlorinated ether contaminants in the US and Europe, and is classified as a B2 carcinogen. In this study, the degradation rate of BCEE by mercury lamps, xenon lamp and electromagnetic induction electrodeless lamp (EIEL) activated persulfate were compared, and EIEL activated persulfate was confirmed to have higher degradation capability and lower energy consumption. In this sense, the degradation kinetics and mechanism in EIEL system were further investigated. The degradation reaction followed pseudo first-order, and the removal rate of BCEE exceeded 95% in 60 min when the initial pH, the concentration of BCEE and Na2S2O8 were 3, 4 mg L-1 and 15 mM, respectively. Presence of inorganic anions and humic acids would reduce the degradation rate constant. In accordance with the results of electron paramagnetic resonance and quenching experiments, SO4-· was dominant in the acidic regime and OH· was dominant in the alkaline regime. Meanwhile, OH· had higher degradation rate with BCEE when initial pH was 7. Seven degradation products were identified and the reaction pathways included OH· substitution and free radical coupling. Although the total organic carbon was eliminated slowly during the degradation of BCEE, the predicted toxicity of most degradation products to Fathead minnow, Daphnia magna and oral rat were lower than BCEE.

Sensitive operation of enzyme-based biodevices by advanced signal processing.

Analytical devices that combine sensitive biological component with a physicochemical detector hold a great potential for various applications, e.g., environmental monitoring, food analysis or medical diagnostics. Continuous efforts to develop inexpensive sensitive biodevices for detecting target substances typically focus on the design of biorecognition elements and their physical implementation, while the methods for processing signals generated by such devices have received far less attention. Here, we present fundamental considerations related to signal processing in biosensor design and investigate how undemanding signal treatment facilitates calibration and operation of enzyme-based biodevices. Our signal treatment approach was thoroughly validated with two model systems: (i) a biodevice for detecting chemical warfare agents and environmental pollutants based on the activity of haloalkane dehalogenase, with the sensitive range for bis(2-chloroethyl) ether of 0.01-0.8 mM and (ii) a biodevice for detecting hazardous pesticides based on the activity of γ-hexachlorocyclohexane dehydrochlorinase with the sensitive range for γ-hexachlorocyclohexane of 0.01-0.3 mM. We demonstrate that the advanced signal processing based on curve fitting enables precise quantification of parameters important for sensitive operation of enzyme-based biodevices, including: (i) automated exclusion of signal regions with substantial noise, (ii) derivation of calibration curves with significantly reduced error, (iii) shortening of the detection time, and (iv) reliable extrapolation of the signal to the initial conditions. The presented simple signal curve fitting supports rational design of optimal system setup by explicit and flexible quantification of its properties and will find a broad use in the development of sensitive and robust biodevices.

Chemical oxidation of bis(2-chloroethyl) ether in the Fenton process: Kinetics, pathways and toxicity assessment.

Bis(2-chloroethyl) ether (BCEE) is a common chemical material and a frequently detected contaminant in groundwater. It has a strong toxicity and some other chemicals such as poly(vinyl chloride-co-isobutyl vinyl ether) contain similar chloroaliphatic ether structure. So the effective degradation method and transformation pathways for BCEE need to be learned. The present study compared the degradation rate of BCEE by Fenton's reagent and other common oxidation methods, and optimized the reaction conditions. Oxidation intermediates and pathways were also proposed and toxicities of the intermediates were investigated. Results showed that Fenton was highly effective to degrade BCEE. pH, Fe2+ and H2O2 concentration all affected the oxidation rate, among which Fe2+ was the most significant variable. A total of twelve chlorinated intermediates were detected. Three main reaction pathways involved cleavage of the ether bond, hydroxyl substitution for hydrogen, and radical coupling. The pathways could be well interpreted and supported by theoretical calculations. The reaction mixture showed a decreasing trend in TOC concentration and toxicity until totally harmless to Vibrio fischeri after 15 min, but it was noteworthy that toxicities of some dimeric intermediates were stronger than BCEE by calculation.

Design, Synthesis, and Biological Evaluation of Novel Benzoyl Diarylamine/ether Derivatives as Potential Anti-HIV-1 Agents.

A series of benzoyl diarylamine/ether derivatives were designed, synthesized, and evaluated for their activity against human immunodeficiency virus (HIV) in MT-4 cells. Three compounds (3b, 5a, and 6a1) exhibited moderate activities against wild-type (wt) HIV-1 with EC50 values ranging from 11 to 56 µm. Among them, compound 5a was the most potent inhibitor with a novel chemical skeleton, affording a new lead compound for further molecular optimization. An enzyme assay was also implemented to confirm the binding target of the active compounds represented by 6a1. Molecular simulation studies on compound 5a, 6a1, and 7a4 were carried out to understand their binding mode with wt HIV-1 reverse transcriptase (RT) and provided useful information for further rational design of NNRTIs.

Synthesis and evaluation of macrocyclic diarylether heptanoid natural products and their analogs.

The macrocyclic diarylether heptanoid (MDEH) natural products have been used in folk medicine for centuries. MDEHs are reported to exert anti-tumor properties by inhibiting the activation of NF-κB. Here we report the synthesis of a small MDEH library (first reported synthesis of racemic platycarynol) using a Grubbs cross metathesis/Ullmann cyclization strategy. Evaluation of the library led to the identification of MDEH 9b which sensitizes pancreatic cancer cells to gemcitabine mediated growth inhibition and apoptosis.

Treatment of persistent organic compounds by integrated advanced oxidation processes and sequential batch reactor.

The objective of this study was to evaluate the extent of improvement in the biodegradability of persistent organic compounds by pre-oxidation by using Sequential Batch Reactors (SBRs). Dichlorodiethyl ether (DCDE), a non-biodegradable compound, was used as a test chemical. Ozonation, Fenton reagent and ultra-violet light coupled with hydrogen peroxide (UV/H(2)O(2)) were used for oxidation of DCDE at levels of 50-100%. Pre-oxidized DCDE solutions were then subjected to SBR studies using activated sludge to determine the rate and extent of biodegradation of oxidation by-products. The results indicated that the biodegradability of pre-oxidized DCDE increased drastically, reaching an average of 90% for all three oxidation methods versus zero for non-oxidized DCDE. It was concluded that the results of SBR experiments may be better indicators of biodegradability of chemically-oxidized wastewaters due to significant acclimation of microorganisms in SBRs, which cannot be observed in conventional respirometric laboratory studies.

Surface catalyzed Fenton treatment of bis(2-chloroethyl) ether and bis(2-chloroethoxy) methane.

This study examined the feasibility of using surface catalyzed Fenton treatment to remediate soil and groundwater contaminated by the chlorinated ethers, bis(2-chloroethyl) ether (BCEE) and bis(2-chloroethoxy) methane (BCEM). Parameters that affect the contaminant loss rate such as porewater pH, hydrogen peroxide concentration, and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil, obtained from an industrial site in Moss Point, MS, that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For a similar set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates (SOURs) were measured for biomass, collected from an activated sludge plant, exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether residual BCEE, BCEM, and their co-contaminants as well as their oxidation by-products were potentially inhibitory or can potentially serve as a substrate for the biomass. The measured SOURs show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the biomass.

Biodegradation of bis(2-chloroethyl) ether by Xanthobacter sp. strain ENV481.

Degradation of bis(2-chloroethyl) ether (BCEE) was observed to occur in two bacterial strains. Strain ENV481, a Xanthobacter sp. strain, was isolated by enrichment culturing of samples from a Superfund site located in the northeastern United States. The strain was able to grow on BCEE or 2-chloroethylethyl ether as the sole source of carbon and energy. BCEE degradation in strain ENV481 was facilitated by sequential dehalogenation reactions resulting in the formation of 2-(2-chloroethoxy)ethanol and diethylene glycol (DEG), respectively. 2-Hydroxyethoxyacetic acid was detected as a product of DEG catabolism by the strain. Degradation of BCEE by strain ENV481 was independent of oxygen, and the strain was not able to grow on a mixture of benzene, ethylbenzene, toluene, and xylenes, other prevalent contaminants at the site. Another bacterial isolate, Pseudonocardia sp. strain ENV478 (S. Vainberg et al., Appl. Environ. Microbiol. 72:5218-5224, 2006), degraded BCEE after growth on tetrahydrofuran or propane but was not able to grow on BCEE as a sole carbon source. BCEE degradation by strain ENV478 appeared to be facilitated by a monooxygenase-mediated O-dealkylation mechanism, and it resulted in the accumulation of 2-chloroacetic acid that was not readily degraded by the strain.

High boron content carboranyl-functionalized aryl ether derivatives displaying photoluminescent properties.

The reaction of alpha,alpha'-bis(3,5-bis(bromomethyl)phenoxy-p-xylene (3) with 4 equiv of the monolithium salt of 1-Ph-1,2-C2B10H11 or 1-Me-1,2-C2B10H11 gave the corresponding neutral carboranyl-functionalized aryl ether derivatives closo-4 and closo-5, respectively. These compounds contain four closo clusters that were degraded using basic conditions with KOH in EtOH, affording the corresponding nido-6 and nido-7 as potassium salts. Nido species were also isolated with tetramethylammonium as cation giving compounds nido-8 and nido-9 in good yield. The potassium salts showed good solubility in water and polar solvents. All these compounds were characterized by 1H, 11B and 13C NMR spectroscopy and UV-vis. The electronic data in different solvents indicated a solvatochromic shift for all compounds and a red shift of the absorption maxima for the nido species with respect to the closo derivatives. These neutral and anionic carboranyl-functionalized aryl ether derivatives represent a new family of high boron content luminescent compounds that show strong fluorescence emission in different solvents at room temperature. This phenomenon is very interesting considering the fact that none of the precursors have such a property. The fluorescence emission depends on the cluster substituent (Ph or Me) and the solvent polarity. Additionally, the fluorescence emission intensity was clearly dependent on the solvent polarity; the closo species showed strongest fluorescence intensities in the non-polar solvents, while anionic species were highly emissive in polar solvents.

Chiral Diphenylprolinol TES ether promoted conjugate addition-aldol-dehydration reactions between alpha,beta-unsaturated aldehydes and 2-N-protected amino benzaldehydes.

A conjugate addition-aldol-dehydration reaction of alpha,beta-unsaturated aldehydes with 2-N-protected amino benzaldehydes has been developed. The process is promoted by (S)-diphenylprolinol TES ether to afford synthetically useful 1,2-dihydroquinolines in high enantioselectivities with good yields. [reaction: see text]

Assessment of enhancement in biodegradation of dichlorodiethyl ether (DCDE) by pre-oxidation.

The objective of this study is to assess the enhancement in biodegradation of dichlorodiethyl ether (DCDE) by ozonation and Fenton treatment. Acclimated and non-acclimated sludge cultures were used to test the biodegradability of the preoxidized DCDE solutions by three different tests: Short-term and long-term respirometry through continuous monitoring of oxygen consumption, and the mid-term test in which the amount of remaining organic matter was measured by TOC and COD tests. These tests were applied to solutions of DCDE preoxidized at the levels of 25%, 50%, 75%, and 100%. The results indicated that the biodegradability of oxidized DCDE solutions improved substantially compared to non-oxidized solutions. Fenton-treated DCDE exhibited toxicity to microorganisms under long-term exposure. Higher levels of preoxidation of DCDE led to mineralization of larger amounts of organic matter during subsequent biodegradation. There was no significant difference in the rate of biodegradation of oxidized products by either acclimated or non-acclimated bacteria.

Organic solvent tolerance of halophilic archaea.

Organic solvent tolerance was tested in type strains of type species of the sixteen genera of Halobacteriaceae, the halophilic archaea. Most of the strains were observed to grow in the presence of hexylether (log Pow=5.1), but none grew in the presence of n-octane (log Pow=4.9) except Halogeometricum borinquense JCM 10706T and Halorubrum saccharovorum JCM 8865T. On the other hand, two strains, Haloarcula spp. OHF-1 and 2 isolated from a French solar salt were found to show stronger tolerance even to isooctane (log Pow=4.8). Growth of some strains was retarded by the presence of n-decane but reached to the same cell densities at late stationary phase. Final cell densities of some strains were greatly repressed by the presence of the solvent.

A comparison of the binding of three series of nicotinic ligands.

A total of 24 aryl-substituted analogues of nicotine (1a) and two related series of nicotinic ligands, aminomethylpyridines 3 and ether analogues 8, were examined to determine if they bind at alpha4beta2 nACh receptors in a common manner. A modest correlation (r=0.785) was found between the affinities of the nicotine analogues and derivatives of 3, but little correlation (r=0.348) was found with analogues 8. However, a modest correlation (r=0.742) exists between the binding of analogues 3 and 8. It seems that 1-series and 8-series compounds bind differently but that the 3-series compounds share some intermediate binding similarity with both.

Design and synthesis of ether analogues as potent and selective M2 muscarinic receptor antagonists.

Novel, selective M2 muscarinic antagonists, which replace the metabolically labile styrenyl moiety of the prototypical M2 antagonist 1 with an ether linkage, were synthesized. A detailed SAR study in this class of compounds has yielded highly active compounds that showed M2 Ki values of < 1.0 nM and >100-fold selectivity against M1, M3, and M5 receptors.

Chemical mutagenesis testing in Drosophila. IX. Results of 50 coded compounds tested for the National Toxicology Program.

Fifty chemicals were tested for mutagenic activity in post-meiotic and meiotic germ cells of male Drosophila melanogaster using the sex-linked recessive lethal (SLRL) assay. As in the previous studies in this series, feeding was chosen as the first route of administration. If the compound failed to induce mutations by this route, injection exposure was used. One gaseous chemical (1,3-butadiene) was tested only by inhalation. Those chemicals that were mutagenic in the sex-linked recessive lethal assay were further tested for the ability to induce reciprocal translocations. Eleven of the 50 chemicals tested were mutagenic in the SLRL assay. These included bis(2-chloroethyl) ether, 1,4-butanediol diglycidyl ether, 1-chloro-2-propanol, dimethyl methylphosphonate, dimethyl morpholinophosphoramidate, dimethyloldihydroxyethylene urea, 2,2-dimethyl vinyl chloride, hexamethylphosphoramide, isatin-5-sulfonic acid (Na salt), isopropyl glycidyl ether, and urethane. Five of these, including 1,4-butanediol diglycidyl ether, 2,2-dimethyl vinyl chloride, hexamethylphosphoramide, isopropyl glycidyl ether, and urethane, also induced reciprocal translocations.

Investigations on metabolism, genotoxic effects and carcinogenicity of 2,2'-dichlorodiethylether.

Either 40 mumole or 160 mumole 2,2'-DDE was injected into male Wistar rats and the metabolites, TdGA and HEMA, were determined in the 24-h urine specimens. Comparative investigations were carried out giving equimolar amounts of chloroethanol and 2-chloroacetaldehyde diethyl acetal. In a further step, inhalation experiments were performed to determine urinary excretion of the two metabolites after an 8-h exposure of male Wistar rats to 10, 50, 100, and 500 ppm 2,2'-DDE and to 50, 200, und 1,000 ppm vinyl chloride. A long-term study was conducted to investigate the possible carcinogenicity of 2,2'-DDE in male and female Sprague-Dawley rats following s.c. injections of 4.36 mumole and 13.1 mumole 2,2'-DDE in DMSO per week. The evaluation of tumor development in treated groups and controls were based on macroscopic inspection and histological examinations of the suspect organs and tissues. Analysis of the metabolites showed that HEMA excretion was much lower than the excretion of TdGA following the uptake of 2,2'-DDE, 2-chloroethanol and 2-chloroacetaldehyde diethyl acetal. Contrary to these, vinyl chloride uptake resulted in a higher urinary excretion of HEMA than TdGA. There was no appreciable increase in the number of tumors detected in 2,2'-DDE-treated animals when compared with untreated or DMSO-treated groups. Since irradiation of 2,2'-DDE with UV did not elevate mutagenic activity of the compound against Salmonella typhimurium TA100, the high mutagenicity of the compound found in a desiccator cannot be due to the liberation of mutagenic compounds produced under the influence of UV light.