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Query: EC:3.4.15.1 (ACE)
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The 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) ionic liquid was immobilized in the pores of a polypropylene hollow fiber for hollow fiber-protected liquid-phase microextraction. Analytes including 4-chlorophenol (4-CP), 3-chorophenol (3-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were extracted into this ionic liquid membrane, and back extracted into 10microL sodium hydroxide acceptor solution in the lumen of the hollow fiber. Then, the acceptor solution was withdrawn into the high-performance liquid chromatography (HPLC) microsyringe connected to the hollow fiber, and directly injected into the HPLC system for analysis. Some parameters that might affect the extraction efficiency were optimized, and low detection limits (0.5microgL(-1) for 4-CP, 3-CP, DCP and 1.0microgL(-1) for TCP) were obtained. Good repeatability was achieved because of the stability of the hollow fiber-supported ionic liquid membrane. The proposed procedure was applied for direct determination of the four chlorophenols in some real water samples including groundwater, river water, wastewater and tap water. All of the four chlorophenols in these water samples were under the limits of determination, and the recoveries were in the range of 70.0-95.7% at 5microgL(-1) spiked level.
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PMID:Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography. 1711 89

An efficient sequential, biological and photocatalytic treatment to reduce the pollutant levels in wastewater due to the bleaching process during paper production is reported. For a biological pre-treatment, 800 ml of non-sterilized effluent was inoculated with Trametes versicolor immobilized in polyurethane foam, with 25 g l(-1) glucose, 6.75 mM CuSO(4), and 0.22 mM MnSO(4) added, and cultured at 25 degrees C with an air flow of 800 ml min(-1) for 8d. The fungus did not inhibit growth of the heterotropic populations of the effluent. After 4d of culture, the chemical oxygen demand (COD) reduction and colour removal (CR) were 82% and 80%, respectively, with laccase (LAC) and manganese peroxidase (MnP) activities of 345 U l(-1) and 78 U l(-1), respectively. The COD reduction and CR correlated positively (p<0.0001) with LAC and MnP activities. Chlorophenol removal was 99% of pentachlorophenol, 99% of 2,3,4,6-tetrachlorophenol (2,3,4,6-TCP), 98% of 3,4-dichlorophenol (3,4-DCP) and 77% of 4-chlorophenol (4-CP), while 2,4,5-trichlorophenol (2,4,5-TCP) increased to 0.2 mg l(-1). The pre-treated effluent was then exposed to a photocatalytic treatment. The treatment with photolysis resulted in 9% CR and 46% COD reduction, 42% CR and 60% COD reduction by photocatalysis, and 62% CR and 85% COD reduction by heterogeneous photocatalysis with the system TiO(2)/Ru(x)Se(y) (Fig. 4). With this treatment the bacterial and fungal populations also decreased by 5 logarithmic units with respect to the biological treatment alone (Fig. 5). The total sequential treatment resulted in a 92% CR (from 5800 UC), 97% COD reduction (from 59 g l(-1)) and 99% chlorophenol removal at 96 h and 20 min.
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PMID:Sequential treatment via Trametes versicolor and UV/TiO2/Ru(x)Se(y) to reduce contaminants in waste water resulting from the bleaching process during paper production. 1712 83

Chlorophenols are one of the most important groups of priority pollutants, due to their high toxicity, mutagenicity and carcinogenicity. Although activated carbon has been the preferred choice for the removal of such pollutants from wastewaters, the search for cheaper alternative sorbents became common in the last years. Fly ash, a by-product from coal burning power plants, has a surface composition that may enable the sorption of specific organic compounds. Therefore, this feasibility study presents the optimization of the operating parameters of a fixed-bed column containing fly ash particles, percolated by aqueous solutions of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) with concentrations of 1 and 100 microg/ml. Both chlorophenols were analysed by gas chromatography with electron capture detection (GC-ECD), after solid-phase microextraction (SPME), with limits of detection (LODs) of 7.28 microg/l for 2,4-DCP and 1.76 microg/l for PCP. Removal efficiencies above 99% were obtained for an initial concentration of 10 microg/ml of chlorophenols. Column saturation was achieved after 7h of continuous operation for 2,4-DCP and 10h for the PCP for feed levels of 10 microg/ml. Fly ash exhibited more affinity towards the sorption of PCP, in comparison to 2,4-DCP.
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PMID:Removal of 2,4-dichlorophenol and pentachlorophenol from waters by sorption using coal fly ash from a Portuguese thermal power plant. 1714 54

Reductive dehalogenase (RD) gene transcript levels in Dehalococcoides ethenogenes strain 195 were investigated using reverse transcriptase quantitative PCR during growth and reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), or 2,3-dichlorophenol (2,3-DCP). Cells grown with PCE or TCE had high transcript levels (greater than that for rpoB) for tceA, which encodes the TCE RD, pceA, which encodes the PCE RD, and DET0162, which contains a predicted stop codon and is considered nonfunctional. In cells grown with 2,3-DCP, tceA mRNA was less than 1% of that for rpoB, indicating that its transcription was regulated. pceA and DET0162 were the only RD genes with high transcript levels in cells grown with 2,3-DCP. Proteomic analysis of PCE-grown cells detected both PceA and TceA with high peptide coverage but not DET0162, and analysis of 2,3-DCP-grown cells detected PceA with high coverage but not TceA, DET0162, or any other potential RD. Cells grown with PCE or 2,3-DCP were tested for the ability to dechlorinate PCE, TCE, or 2,3-DCP with H2 as the electron donor. 2,3-DCP-grown cells were unable to dechlorinate TCE but dechlorinated PCE to TCE without a lag, and PCE-grown cells dechlorinated 2,3-DCP without a lag. These results show that 2,3-DCP-grown cells do not produce TceA and that DET0162 is transcribed but its translation product is not detectable in cells and are consistent with PceA's being bifunctional, also serving as the 2,3-DCP RD. Chlorophenols naturally occur in soils and are good candidates for the original substrates for PceA.
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PMID:Expression of reductive dehalogenase genes in Dehalococcoides ethenogenes strain 195 growing on tetrachloroethene, trichloroethene, or 2,3-dichlorophenol. 1751 89

The catalytic dechlorination of five chlorophenols, by Ni/Fe bimetal was investigated through batch experiments. The results showed that the destruction of chlorophenols by hydrodechlorination over Ni / Fe was very effective and followed the pseudo-first-order kinetics under aqueous conditions. The order of reaction rate was 2-chlorophenol > 4-chlorophenol > 2,4-dichlorophenol > 2,4,6-trichlorophenol > 2,6-dichlorophenol (2,6-DCP). The dechlorination rate of chlorophenol increased linearly with increasing nickel coating on iron. In general, increasing the degree of chlorine substitution on the phenol ring decreased the rate of dechlorination except for 2,6-DCP. Chlorophenols were dechlorinated to phenol via both stepwise as the major pathway and concerted mechanisms with minor contribution. The relative contribution of each reaction pathway is discussed through a model fitting.
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PMID:Kinetic studies of reductive dechlorination of chlorophenols with Ni/Fe bimetallic particles. 1761 67

The goal of the present study was to assess the possibility to change the composition of a calcium phosphate scaffold from a high-temperature phase to a phase only stable at or close to room temperature without macrostructural changes. For that purpose, macroporous beta-TCP scaffolds were converted into alpha-TCP by high-temperature thermal treatment and then dipped into a phosphoric acid solution to obtain a more acidic calcium phosphate phase called monetite or dicalcium phosphate (DCP; CaHPO4). Two different solid-to-liquid ratios (SLR: 0.067 and 0.200g/mL) and three different temperatures (T: 37, 60 and 80 degrees C) were used. The reaction was followed by measuring the change of sample size and weight, by determining the compositional changes by X-ray diffraction (Rietveld analysis), and by looking at the micro- and macrostructural changes by scanning electron microscopy and micro-computed tomography. The results revealed that the transformation proceeded faster at a higher temperature and a higher SLR value but was achieved within a few days in all cases. Morphologically, the porosity decreased by 10%, the pore size distribution became wider and the mean macro pore size was reduced from 0.28 to 0.19mm. The fastest conversion and the highest compressive strength (9MPa) were measured using an incubation temperature of 80 degrees C and an SLR value of 0.2g/mL.
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PMID:Bone substitute: transforming beta-tricalcium phosphate porous scaffolds into monetite. 1849 42

Determination of trace chlorophenols (CPs) in environmental samples has been evaluated using liquid-phase microextraction (LPME) coupled with gas chromatography-mass spectrometry (GC-MS) without derivatization. The LPME procedure used to extract CPs from water involved 15 microL 1-octanol as acceptor solution in a 5.0 cm polypropylene hollow fiber with an inner diameter of 600 microm and a pore size of 0.2 microm. Under the optimal extraction conditions, enrichment factors from 117 to 220 are obtained. The obtained linear range is 1-100 ng mL(-1) with r(2)=0.9967 for 2,4-dichlorophenol (2,4-DCP); 1-100 ng mL(-1) with r(2)=0.9905 for 2,4,6-trichlorophenol (2,4,6-TCP); 5-500 ng mL(-1) with r(2)=0.9983 for 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and 10-1000 ng mL(-1) with r(2)=0.9929 for pentachlorophenol (PCP). The limits of detection range from 0.08 to 2 ng mL(-1), which is comparable with the reported values (12-120 ng mL(-1)). Recoveries of CPs in various matrices exceed 85% with relative standard deviations of less than 10%, except for PCP in landfill leachate. The applicability of this method was examined to determine CPs in environmental samples by analyzing landfill leachate, ground water and soil. The 2,4-DCP and 2,4,6-TCP detected in the landfill leachate are 6.68 and 2.47 ng mL(-1). The 2,4,6-TCP detected in ground water is 2.08 ng mL(-1). All the studied CPs are detected in contaminated soil. The proposed method is simple, low-cost, less organic solvent used and can potentially be applied to analyze CPs in complex environmental matrices.
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PMID:Evaluation of liquid-phase microextraction conditions for determination of chlorophenols in environmental samples using gas chromatography-mass spectrometry without derivatization. 1858 57

This study reports the feasibility of removing pentachlorophenol (PCP) by an acidogenic process in batch reactors. When the acidogenic sludge was first acclimated with 2,4,6-trichlorophenol (2,4,6-TCP) and developed 2,4,6-TCP dechlorinating activity, PCP could be ortho-dechlorinated to 3,4,5,-trichlorophenol (3,4,5-TCP) via 2,3,4,5-tetrachlorophenol as the intermediary. However, due to PCP's higher hydrophobicity and its higher expected Gibbs free energy yield, it was adsorbed to the sludge and dechlorinated preferentially to 2,4,6-TCP. This resulted in the inhibition of 2,4,6-TCP dechlorination. PCP removal under acidogenic condition was attributed to both reductive dechlorination and adsorption. At low PCP loads of 0.48micromoles/gMLVSS.d, dechlorination was the dominant removal mechanism (69% of total removal), while at the higher PCP load of 9.3micromoles/gMLVSS.d, adsorption was the main mechanism (82% of total removal). Attempts to induce meta or para position dechlorination of PCP failed when using meta position chlorophenols such as 2,3,6-TCP, 3,4,5-TCP and 3,5-DCP as the initial substrates. Overall, acidogenic biotreatment was an effective process in reducing PCP loads prior to downstream biological treatment.
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PMID:Pentachlorophenol dechlorination by an acidogenic sludge. 1869 30

A modified headspace liquid-phase microextraction (HS-LPME) method was studied for the extraction of chlorophenols (CPs) from aqueous samples with complicated matrices, before gas chromatographic (GC) analysis with electron capture detection (ECD). Microwave heating was applied to accelerate the evaporation of CPs into the headspace, and an external-cooling system was used to control the sampling temperature. Conditions influencing extraction efficiency, such as the LPME-solvent, the sampling position of LPME, the sampling temperature, microwave power, and irradiation time (the same as sampling time), sample pH, and salt addition were thoroughly optimized. Experimental results indicated that the extraction of CPs from a 10mL aquatic sample (pH 1.0) was achieved with the best efficiency through the use of 1-octanol as solvent, microwave irradiation of 167W, and sampling at 45 degrees C for 10min. The detections were linear in the concentration of 5.0-100microg/L for 2,4-dichlorophenol (2,4-DCP), and 0.5-10microg/L for 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP). Detection limits were found to be 0.7, 0.04, 0.07, and 0.08microg/L for 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP, and PCP, respectively. A landfill leachate sample was analyzed with recovery between 83 and 102%. The present method was proven to serve as a simple, sensitive, and rapid procedure for CP analysis in an aqueous sample.
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PMID:Microwave-assisted headspace controlled temperature liquid-phase microextraction of chlorophenols from aqueous samples for gas chromatography-electron capture detection. 1876 Jul 97

Chlorophenols are potentially harmful pollutants that are found in numerous natural and agricultural systems. Plants are a sink for xenobiotics, which occur either intentionally or not, as they are unable to eliminate them although they generally metabolize them into less toxic compounds. The metabolic fate of [ (14)C] 4-chlorophenol (4-CP), [ (14)C] 2,4-dichlorophenol (2,4-DCP), and [ (14)C] 2,4,5-trichlorophenol (2,4,5-TCP) was investigated in lettuce, spinach, and radish to locate putative toxic metabolites that could become bioavailable to food chains. Radish plants were grown on sand for four weeks before roots were dipped in a solution of radiolabeled chlorophenol. The leaves of six-week old lettuce and spinach were treated. Three weeks after treatments, metabolites from edible plant parts were extracted and analyzed by high performance liquid chromatography (HPLC) and characterized by mass spectrometry (MS), and nuclear magnetic resonance spectroscopy (NMR). Characterization of compounds highlighted the presence of complex glycosides. Upon hydrolysis in the digestive tract of animals or humans, these conjugates could return to the toxic parent compound, and this should be kept in mind for registration studies.
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PMID:Metabolic fate of [14C] chlorophenols in radish (Raphanus sativus), lettuce (Lactuca sativa), and spinach (Spinacia oleracea). 1876 82


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