Inhibition of diethyl ether degradation in Rhodococcus sp. strain DEE5151 by glutaraldehyde and ethyl vinyl ether

Alkyl ether-degrading Rhodococcus sp. strain DEE5151, isolated from activated sewage sludge, has an activity for the oxidation of a variety of alkyl ethers, aralkyl ethers and dibenzyl ether. The whole cell activity for diethyl ether oxidation was effectively inhibited by 2,3-dihydrofurane, ethyl vinyl ether and glutaraldehyde. Glutaraldehyde of less than 30 microM inhibited the activity by a competitive manner with the inhibition constant, K(I) of 7.07+/-1.36 microM. The inhibition type became mixed at higher glutaraldehyde concentrations >30 microM, probably due to the inactivation of the cell activity by the Schiff-base formation. Structurally analogous ethyl vinyl ether inhibited the diethyl ether oxidation activity in a mixed manner with decreasing the apparent maximum oxidation rate, v(max)(app), and increasing the apparent Michaelis-Menten constant, K(M)(app). The mixed type inhibition by ethyl vinyl ether seemed to be introduced not only by the structure similarity with diethyl ether, but also by the reactivity of the vinyl ether with cellular components in the whole cell system.     

Mutagenicity of aromatic glycidyl ethers with Salmonella

6 aromatic glycidyl ethers containing naphthyl, biphenyl or benzylphenyl substituents were synthesized. These epoxides together with the commercially available compounds 2-biphenylyl glycidyl ether were examined for dose-mutagenicity relationships using the plate incorporation Ames test with Salmonella typhimurium strains TA100 and TA1535. Structure-mutagenicity relationships were further examined for these compounds and 3 phenyl glycidyl ethers by concurrent testing at a single dose with strain TA100. Meaningful correlations could not be established for the mutagenicity of these epoxides to their molecular volumes, partition values, nor to their reactivities with the model nucleophile, 4-(4-nitrobenzyl) pyridine. However, it was noted that increased conjugated aromatic unsaturation with its resulting planarity led to increased mutagenicity and that this effect decreased when it was further removed from the epoxide moiety.     

Bacterial degradation of glycol ethers

Assimilation of ethyleneglycol (EG) ethers by polyethyleneglycol-utilizing bacteria was examined. Ethyleneglycol ether-utilizing bacteria were also isolated from soil and activated sludge samples by enrichment-culture techniques. Three strains (4-5-3, EC 1-2-1 and MC 2-2-1) were selected and characterized as Pseudomonas sp. 4-5-3, Xanthobacter autotrophicus, and an unidentified gram-negative, non-spore-forming rod respectively. Their growth characteristics were examined: Pseudomonas sp. 4-5-3 assimilated EG (diethyleneglycol, DEG) monomethyl, monoethyl and monobutyl ethers, DEG, propanol and butanol. X. autotrophicus EC 1-2-1 grew well on EG monoethyl and monobutyl ethers, EG and primary alcohols (C₁-C₄), and slightly on EG monomethyl ether. The strain MC 2-2-1 grew on EG monomethyl ether, EG, primary alcohols (C₁-C₄), and 1,2-propyleneglycol (PG). The mixed culture of Pseudomonas sp. 4-5-3 and X. autotrophicus EC 1-2-1 showed better growth and improved degradation than respective single cultures towards EG monomethyl, monoethyl or monobutyl ethers. Intact cells of Pseudomonas sp. 4-5-3 degraded various kinds of monoalkyl ethers, which cannot be assimilated by the strain. Metabolic products were characterized from reaction supernatants of intact cells of Pseudomonas sp. 4-5-3 with EG or DEG monoethyl ethers: they were analyzed by thin-layer chromatography and GC-MS and found to be ethoxyacetic acid and ethoxyglycoxyacetic acid. Also, PG monoalkyl ethers (C₁-C₄), dipropyleneglycol monoethyl and monomethyl ethers and tripropyleneglycol monomethyl ether were assimilated by polypropyleneglycol-utilizing Corynebacterium sp. 7.     

Mutagenicities of glycidyl ethers for Salmonella typhimurium: relationship between mutagenic potencies and chemical reactivity

The lethal and mutagenic effects of ethyl, benzyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl and 9-anthrylmethyl glycidyl ethers on Salmonella typhimurium (TA100, TA1535, TA98 and TA1538) were investigated. LD30-value became smaller with an increase in compound hydrophobicity. The mutagenicities of these compounds in TA100 increased in the order: 1-naphthylethyl glycidyl ether less than 2-naphthylethyl glycidyl ether less than benzyl glycidyl ether less than 2-naphthylmethyl glycidyl ether less than 1-naphthylmethyl glycidyl ether less than 9-anthrylmethyl glycidyl ether. 1-Naphthylmethyl and 2-naphthylmethyl glycidyl ethers were mutagenic toward TA1535. In TA98, 1-naphthylmethyl and 9-anthrylmethyl glycidyl ethers showed mutagenic activity and 9-anthrylmethyl glycidyl ether was more mutagenic than 1-naphthylmethyl glycidyl ether. 9-Anthrylmethyl glycidyl ether was also active in TA1538. In the reaction of glycidyl ethers with deoxyguanosine and related compounds, glycidyl ethers attacked at only N-7 of guanine. The alkylation rates of glycidyl ethers toward guanine residues in DNA were determined and the exciplex-formation ability of 7-substituted guanines was studied. The reactivity of glycidyl ethers with guanine residues in DNA has not provided a sufficient explanation for the variation in mutagenic potencies of glycidyl ethers.     

Metabolism of Diethyl Ether and Cometabolism of Methyl tert-Butyl Ether by a Filamentous Fungus, a Graphium sp

In this study, evidence for two novel metabolic processes catalyzed by a filamentous fungus, Graphium sp. strain ATCC 58400, is presented. First, our results indicate that this Graphium sp. can utilize the widely used solvent diethyl ether (DEE) as the sole source of carbon and energy for growth. The kinetics of biomass accumulation and DEE consumption closely followed each other, and the molar growth yield on DEE was indistinguishable from that with n-butane. n-Butane-grown mycelia also immediately oxidized DEE without the extracellular accumulation of organic oxidation products. This suggests a common pathway for the oxidation of both compounds. Acetylene, ethylene, and other unsaturated gaseous hydrocarbons completely inhibited the growth of this Graphium sp. on DEE and DEE oxidation by n-butane-grown mycelia. Second, our results indicate that gaseous n-alkane-grown Graphium mycelia can cometabolically degrade the gasoline oxygenate methyl tert-butyl ether (MTBE). The degradation of MTBE was also completely inhibited by acetylene, ethylene, and other unsaturated hydrocarbons and was strongly influenced by n-butane. Two products of MTBE degradation, tert-butyl formate (TBF) and tert-butyl alcohol (TBA), were detected. The kinetics of product formation suggest that TBF production temporally precedes TBA accumulation and that TBF is hydrolyzed both biotically and abiotically to yield TBA. Extracellular accumulation of TBA accounted for only a maximum of 25% of the total MTBE consumed. Our results suggest that both DEE oxidation and MTBE oxidation are initiated by cytochrome P-450-catalyzed reactions which lead to scission of the ether bonds in these compounds. Our findings also suggest a potential role for gaseous n-alkane-oxidizing fungi in the remediation of MTBE contamination.     

Biodegradation of diphenyl ethers by a copper-resistant mutant ofErwinia sp.

Summary A bacterium tentatively identified as anErwinia sp. was isolated from sewage by enrichment on methanol and lignin. Several mutants developed from this strain were studied for their ability to degrade aromatic ethers. Different concentrations of the chemicals were incubated with the organisms and the degradation was estimated by high-performance liquid chromatography (HPLC). Among these mutants, one isolate,Erwinia sp. strain CU3614, showed resistance to copper ions (>20 mM CuSO₄) and the ability to degrade 4-hydroxydiphenyl ether (4-HDPE), 4-chlorodiphenyl ether (4-CDPE), 4-nitrodiphenyl ether (4-NDPE) and 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) in the presence of copper ions. Increased concentrations of copper in the medium resulted in higher degradation of 4-HDPE. Further studies with copper-sensitive mutants obtained fromErwinia sp. CU3614 by Tn5 transposon-induced mutagenesis showed a corresponding decrease in the ability to degrade 4-HDPE. These results suggest the presence of a copper-associated activity in the biotransformation of aromatic ethers.     

Scopoletin sesquiterpene ethers from Artemisia persica

The roots of Artemisia persica afforded in addition to isofraxidin-derived sesquiterpene ethers, the scopoletin farnesyl ether scopofarnol and the new scopoletin drimenyl ether scopodrimol A. The structures and stereochemistries were elucidated by spectroscopic methods. According to the leaf morphology the accumulation of coumarin sesquiterpene ethers also suggests that the species should be transferred from the section Absinthium to the section Abrotanum.     

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [³H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [³H]cholesteryl oleoyl ether and [³H]cholesteryl hexadecyl ether from different suppliers, employing in vitro, in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro, in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.     

Catabolism of arylglycerol-beta-aryl ethers lignin model compounds by Pseudomonas cepacia 122

Pseudomonas cepacia 122 can grow on several lignin model compounds including the arylglycerol-beta-aryl ethers guaiacylglycerol-beta-coniferyl ether and guaiacylglycerol-beta-guaiacyl ether. Non-phenolic lignin model compounds are not degraded by this bacterium. The enzyme system catalyzing guaiacylglycerol-beta-guaiacyl ether dissimilation in Pseudomonas cepacia 122 is inducible and repressed by glucose. Guaiacylglycerol and guaiacylglycerol-beta-guaiacyl ether were identified as intermediates in guaiacylglycerol-beta-coniferyl ether catabolism. Guaiacol, guaiacoxyethanol, vanillin and vanillic acid were identified as intermediates of guaiacylglycerol-beta-guaiacyl ether breakdown indicating that a C alpha-C beta splitting mechanism is involved in the degradation of aryl-alkyl ethers by this bacterium.     

Triterpene methyl ethers of Chionochloa (Gramineae)

The leaf wax of twenty species of Chionochloa was examined for triterpene methyl ethers; twelve species gave positive yields. The known pentacyclic methyl ethers arundoin, miliacin, lupeol methyl ether and β-amyrin methyl ether were identified and the methyl ethers of the tetracyclic alcohols, cycloartenol and parkeol are reported as new natural products. Arundoin and miliacin occur in many species while the remaining compounds may be suitable chemotaxonomic markers.     

The glyceryl ethers of Paramecium phospholipids and phosphonolipids

Two glyceryl ethers, 1-O-hexadecyl glycerol and 1-O-cis-octadec-11-enyl glycerol, chimyl and paramecyl alcohol, respectively, were quantified in total phospholipids and five glycerophospholipid classes from cells and cilia of the ciliated protozoon, Paramecium tetraurelia. The ether content of 2-aminoethyl phosphonoglycerolipid was 85-90 mole %. Concentrations of ethers were greatest in the ethanolamine phosphonolipids greater than phosphatidylcholines greater than phosphatidylserines greater than phosphatidylethanolamines greater than phosphatidylinositols. The glyceryl ether concentrations in total cellular phospholipids increased with culture age in P. tetraurelia and P. multimicronucleatum cells. The glyceryl ether concentrations in the phospholipids of P. tetraurelia cilia remained constant from mid log to stationary phase of culture growth. Paramecium tetraurelia phospholipid glyceryl ether concentrations were made greater by supplementation of cultures with chimyl alcohol.     

Transformation of diphenyl ethers by Trametes versicolor and characterization of ring cleavage products

The white-rot fungi Trametes versicolor SBUG 1050, DSM 11269 and DSM 11309 are able to oxidize diphenyl ether and its halogenated derivatives 4-bromo- and 4-chlorodiphenyl ether. The products formed from diphenyl ether were 2- and 4-hydroxydiphenyl ether. Both 4-bromo- and 4-chlorodiphenyl ether were transformed to the corresponding products hydroxylated at the non-halogenated ring. Additionally, ring-cleavage products were detected by high perfomance liquid chromatography and characterized by gas chromatography/mass spectrometry and proton nuclear magnetic resonance spectroscopy. Unhalogenated diphenyl ether was degraded to 2-hydroxy-4-phenoxymuconic acid and 6-carboxy-4-phenoxy-2-pyrone. Brominated derivatives of both these compounds were formed from 4-bromodiphenyl ether, and 4-chlorodiphenyl ether was transformed in the same way to the analogous chlorinated ring cleavage products. Additionally, 4-bromo- and 4-chlorophenol were detected as intermediates from 4-bromo- and 4-chlorodiphenyl ether, respectively. In the presence of the cytochrome-P450 inhibitor 1-aminobenzotriazole, no metabolites were formed by cells of Trametes versicolor from the diphenyl ethers investigated. Cell-free supernatants of whole cultures with high laccase and manganese peroxidase activities were not able to transform the unhydroxylated diphenyl ethers used.     

Synthesis, DNA cleavage, and cytotoxicity of a series of bis(propargylic) sulfone crown ethers

Compounds that couple molecular recognition of specific alkali metal ions with DNA damage may display selective cleavage of DNA under conditions of elevated alkali metal ion levels reported to exist in certain cancer cells. We have prepared a homologous series of compounds in which a DNA reactive moiety, a bis(propargylic) sulfone, is incorporated into an alkali metal ion binding crown ether ring. Using the alkali metal ion pricrate extraction assay, the ability of these crown ethers to bind Li(+), Na(+), and K(+) ions was determined. For the series of crown ethers, the association constants for Li(+) ions are generally low (< 2 x 10(4)M(-1)). Only two of the bis(propargylic) sulfone crown ethers associate with Na(+) or K(+) ions (K(a) 4-8 x 10(4)M(-1)), with little discrimination between Na(+) or K(+) ions. The ability of these compounds to cleave supercoiled DNA at pH 7.4 in the presence of Li(+), Na(+), and K(+) ions was determined. The two crown ethers that bind Na(+) and K(+) display a modest increase in DNA cleavage efficiency in the presence of Na(+) or K(+) ions as compared to Li(+) ions. These two bis(propargylic) sulfone crown ethers are also more cytotoxic against a panel of human cancer cell lines when compared to a non-crown ether macrocyclic bis(propargylic) sulfone.     

A simple method for the synthesis of cholesteryl ethers

A novel method for the synthesis of cholesteryl ethers is described. The mesylates of fatty alcohols were treated with the sodium salt of cholesterol in toluene at 80 degrees C in the presence of anhydrous dimethyl formamide. The hexyl, tetradecyl, and oleyl cholesteryl ethers were synthesized in yields varying between 55 and 70%. Tritiated cholesteryl oleyl ether was also synthesized in good chemical (45%) and radiochemical (45%) yields.     

Metabolism of symmetrical dialkyl ethers by Acinetobacter sp. HO1-N

The growth of Acinetobacter species HO1-N on a homologous series of dialkyl ethers yielded characteristic cellular and extracellular ether fatty acids. Microbial growth on diheptyl ether resulted in the appearance of 7-n-heptoxy-1-n-heptanoic acid as a cellular fatty acid and 2-n-heptoxy-1-acetic acid as the sole extracellular fatty acid. The oxidation of dinonyl ether and didecyl ether by Acinetobacter resulted in the extracellular accumulation of 2-n-nonoxy-acetic acid and 2-n-decoxy-1-acetic acid, respectively. The 16-carbon ether fatty acid, 6-n-decoxy-1-n-hexanoic acid, was identified as a major cellular fatty acid in didecyl ether-grown cells. The extracellular ether fatty acids accumulated in an inverse relationship to the disappearance of the dialkyl ether and appeared to represent end products of metabolism. The carbon and energy required for cellular growth and metabolism resided in the terminal 5-carbons of diheptyl ether, 7-carbons of dinonyl ether and 8-carbons of didecyl ether. Glutarate, adipate, pimelate and suberate were identified from cells grown at the expense of diheptyl, dioctyl, dinonyl and didecyl ether, respectively, suggesting a role for dibasic acids as metabolic intermediates. A new and novel mechanism for the metabolism of symmetrical dialkyl ethers is suggested. Terminal methyl group oxidation of the dialkyl ether results in the formation of an alkoxy-fatty acid followed by an internal carbon-carbon scission reaction 2-carbons removed from the oxygen atom. The resulting endproducts are alkoxyacetic acid and the corresponding dibasic acid.Non-Standard Abbreviations TLC Thin Layer Chromatography - PS-DEGS · PS Diethylene glycol succinate - DHE Diheptyl ether - DOE Dioctyl ether - DNE Dionyl ether - DDE Didecyl ether     

Sesquiterpene-coumarin ethers and polyacetylenes from Bfrocchia cinerea

The roots of Brocchia cinerea afforded, in addition to known spiroketalenolether polyynes and sesquiterpene-coumarin ethers, two new isofraxidin-derived sesquiterpene ethers as well as the new 8-farnesyl-scopoletin. The structures of the new compounds were elucidated on the basis of spectroscopic evidence. The chemotaxonomic significance of sesquiterpene-coumarin ether and spiroketalenolether accumulation within the tribe Anthemideae is discussed.     

Relative teratogenicity of nitrofen analogs in mice: unchlorinated, monochlorinated, and dichlorinated-phenyl ethers

To determine the role of number and position of chlorine substituents on the developmental toxicity of diphenyl ether analogs of nitrofen, we have evaluated one unchlorinated, three monochlorinated, and five dichlorinated-phenyl 4'-nitrophenyl ethers with respect to effects on liver weight and on maintenance of pregnancy in females, and with respect to postnatal survival and the occurrence of small or absent Harderian glands in offspring. None of the diphenyl ethers evaluated in these experiments was as active as nitrofen with respect to any parameter evaluated. Both the position and the number of chlorine substituents affected toxicity, but no simple relationship between number or position of chlorine substituents and either maternal or fetal endpoints was established.     

Study of hydrolysis of aminoalcohol ethers, phenol and choline under the action of horse blood serum cholinesterase]

Hydrolysis of ethers of saturated and unsaturated alcohols and ethers, e.g. phenol and choline, under the action of horse blood serum cholinesterase, was studied. The reactivity towards enzymatic hydrolysis is decreased due to a greater length of the chain in the alcohol residue of the benzoic acid aminoethers; at nCH2 = 4 the compound is a poor substrate. An increase in nydrophobicity of the acyl residue of the ether molecule also leads to a decrease in the Vmax and Km values. In case of cholinesterase substrates, an increase in the molecule hydrophobicity results in an increase of its non-productive absorption on the active surface of the enzyme, which decreases its hydrolysis. Aminobutynol benzoates are hydrolyzed by cholinesterase more rapidly as compared to the ethers of corresponding aminobutanols and their homologs.     

Isolation and identification of cholesteryl alkyl ethers from bovine cardiac muscle

Cholesteryl alkyl ethers have been isolated from bovine cardiac muscle and characterized by thin-layer and gas-liquid chromatography. The fraction contained at least three homologues. Cholesteryl hexadecyl ether, which accounted for over 90% of the total components observed on gas chromatography, was identified by mass spectrometry.     

Effect of second-sphere coordination 12. Adduct formation behavior of crown ethers with ammine complexes of ruthenium containing a protic ligand of other type than ammine

Adduct formation of pentaammineruthenium complexes involving a different type of protic ligand, such as imidazole, was investigated for a series of crown ethers with different ring size. Changes in redox potential and in absorption spectra of the complex were measured on addition of crown ether to the complex solution. The magnitude of the change in both properties is dependent on the ring size of crown ethers. ¹H-NMR spectra of the complex were measured in the presence of crown ethers in order to elucidate hydrogen bonding sites. The chemical shifts of NH proton of imidazol and ammine protons were measured at various concentrations of crown ethers. Adduct formation was discussed based on the features of dependences of those chemical shifts on crown ether concentration.